Heterocyclic pyrazoline carboxanilides

ABSTRACT

Heterocyclic pyrazoline carboxanilide insecticides including all geometric and stereoisomers thereof, as well as agricultural compositions containing them.

This is a continuation of Ser. No. 126,619 filed Nov. 30, 1987, nowabandoned.

BACKGROUND OF THE INVENTION

Compounds and compositions comprising heterocyclic pyrazolinecarboxanilides having a >N--N═C--C(O or S)--N< backbone.

J. Org. Chem., 20, page 1619 (1955) discloses1,5-diphenyl-2-pyrazoline-3-carboxamide. No utility is presented.Harhash et al., J. Heterocyclic Chem., 21, page 1013 (1984), disclosethe preparation of these five pyrazolines for which no utility ispresented: ##STR1## where R/Ar are C₆ H₅ /C₆ H₅, CO₂ C₂ H₅ /C₆ H₅,C(O)NHC₆ H₅ /C₆ H₅, CH═CHC₆ H₅ /C₆ H₅ and CH₃ /4--NO₂ --C₆ H₄.

U.S. Pat. No. 4,070,365 discloses insecticidal compounds of the formula##STR2## where R₁ is optionally substituted phenyl; R₂ and R₃ areindependently optionally substituted pyridyl, thienyl or phenyl groupsand X is O or S.

EPA 0153127 discloses insecticidal compounds of the formula ##STR3##wherein A and B are unsubstituted or substituted aryl; U is O, S or NR;Y is alkyl, carbonyl or unsubstituted or substituted aryl, and Z iscycloalkyl or an unsubstituted or substituted aryl group.

PCT International Publication No. WO88/05046 discloses pyrazolineinsecticides of the formula ##STR4## wherein: A is H, C₁ to C₆ alkyl,phenyl, phenyl substituted by (R₅)_(p), CN, CO₂ R₃, C(O)R₃, C(O)NR₃ R₄,C(S)NR₃ R₄, C(S)R₃ or C(S)SR₃ ;

B is H, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₂ to C₆ alkoxyalkyl, C₂ toC₆ cyanoalkyl, C₃ to C₈ alkoxycarbonylalkyl, C₂ to C₆ alkenyl, C₂ to C₆alkynyl, C₂ to C₆ alkoxycarbonyl, phenyl, phenyl substituted with 1 to 3substituents independently selected from W, benzyl or benzyl substitutedwith 1 to 3 substituents independently selected from W.

SUMMARY OF THE INVENTION

This invention pertains to compounds of Formula I, including allgeometric and stereoisomers thereof, agriculturally suitable saltsthereof, agricultural compositions containing said compounds and salts,and their use as insecticides: ##STR5## wherein: X is O or S;

Y is selected from the group H, C₁ to C₄ alkyl, C₂ to C₄ alkoxyalkyl, C₁to C₄ alkylthio, C₁ to C₄ haloalkylthio, SX', phenylthio, or phenylthiosubstituted with 1 to 3 substituents independently selected from W, C₂to C₄ alkoxycarbonyl, C(O)H, C₂ to C₄ alkylcarbonyl and C₂ to C₄haloalkylcarbonyl;

A is selected from the group H, C₁ to C₆ alkyl, phenyl, phenylsubstituted by (R₅)_(p), CN, CO₂ R₃, C(O)R₃, C(O)NR₃ R₄, C(S)NR₃ R₄,C(S)R₃, C(S)SR₃ and J;

B is selected from the group H, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₂to C₆ alkoxyalkyl, C₂ to C₆ cyanoalkyl, C₃ to C₈ alkoxycarbonylalkyl, C₂to C₆ alkenyl, C₂ to C₆ alkynyl, C₂ to C₆ alkoxycarbonyl, phenyl, phenylsubstituted with 1 to 3 substituents independently selected from W,benzyl and benzyl substituted with 1 to 3 substituents independentlyselected from W;

W is selected from the group halogen, CN, NO₂, C₁ to C₂ alkyl, C₁ to C₂haloalkyl, C₁ to C₂ alkoxy, C₁ to C₂ haloalkoxy, C₁ to C₂ alkylthio, C₁to C₂ haloalkylthio, C₁ to C₂ alkylsulfonyl and C₁ to C₂haloalkylsulfonyl;

R is ##STR6## or K, being K when A is other than J; R₁, R₂ and R₅ areindependently selected from the group R₃, halogen, CN, N₃, SCN, NO₂,OR₃, SR₃, S(O)R₃, S(O)₂ R₃, OC(O)R₃, OS(O)₂ R₃, CO₂ R₃, C(O)R₃, C(O)NR₃R₄, S(O)₂ NR₃ R₄, NR₃ R₄, NR₄ C(O)R₃, OC(O)NHR₃, NR₄ C(O)NHR₃, NR₄ S(O)₂R₃, and when m, n or p is 2, R₁, R₂ or R₅ can be taken together as--OCH₂ O--, --OCF₂ O--, --OCH₂ CH₂ O--, --CH₂ C(CH₃)₂ O--, --OCF₂ CF₂O--, or --CF₂ CF₂ O-- to form a 5- or 6-membered ring;

R₃ is selected from the group H, C₁ to C₄ alkyl, C₁ to C₄ haloalkyl, C₂to C₄ alkenyl, C₂ to C₄ haloalkenyl, C₂ to C₄ alkynyl, C₂ to C₄haloalkynyl, C₂ to C₄ alkoxyalkyl, C₂ to C₄ alkylthioalkyl, C₁ to C₄nitroalkyl, C₁ to C₄ cyanoalkyl, C₃ to C₆ alkoxycarbonylalkyl, C₃ to C₆cycloalkyl, C₃ to C₆ halocycloalkyl, phenyl, benzyl, or phenyl or benzylsubstituted with 1 to 3 substituents independently selected from W;

R₄ is H or C₁ to C₄ alkyl, or when R₃ and R₄ are attached to a singlenitrogen atom, they can be taken together as ##STR7## J and K areindependently selected from a 5- or 6-membered heteroaromatic ringsindependently containing 1 or 2 heteroatoms independently selected from0 to 1 oxygen, 0 to 1 sulfur and 0 to 2 nitrogen atoms, attached viacarbon and optionally substituted by one or more substituentsindependently selected from W;

X' is ##STR8## R₆ and R₁₀ are independently selected from C₁ to C₆alkyl, C₁ -C₆ haloalkyl, C₃ -C₆ cycloalkyl, C₄ -C₇ cycloalkylalkyl, C₂to C₆ cyanoalkyl, C₂ to C₆ alkoxyalkyl, C₃ to C₈ alkoxycarbonylalkyl, C₄to C₈ dialkylaminocarbonylalkyl, phenyl optionally substituted by 1 to 2substituents selected from W, benzyl optionally substituted by 1 to 2substituents selected from W, and phenethyl optionally substituted by 1to 2 substituents selected from W, or R₆ and R₁₀ can be taken togetheras (CH₂)₄, (CH₂)₅ or (CH₂)₂ O(CH₂)₂, each ring being optionallysubstituted with 1 to 2 CH₃ ;

R₇ is F, C₁ -C₂₀ alkyl, C₁ -C₆ haloalkyl, C₂ -C₈ dialkylamino, ##STR9##each ring being optionally substituted with 1 to 2 CH₃ ; phenyloptionally substituted by 1 to 2 substituents selected from W, or R₇ isC₁ -C₂₀ alkoxy, C₁ -C₄ alkoxy substituted by cyano, nitro, C₁ -C₄alkoxy, C₄ -C₈ alkoxyalkoxy, C₁ -C₂ alkylthio, C₂ -C₃ alkoxycarbonyl, C₃-C₅ dialkylaminocarbonyl, phenyl or 1 to 6 halogens, or R₇ is phenoxyoptionally substituted by 1 to 2 substituents selected from W,

R₈ and R₉ are independently selected from C₁ -C₄ alkyl, C₂ -C₄ haloalkylor phenyl optionally substituted by 1 to 2 substituents selected from Wor R₈ and R₉ may be taken together as (CH₂)₂, (CH₂)₃ or CH₂ C(CH₃)₂ CH₂;

a is 0 to 2;

Y' is O or S;

m is 1 to 3;

n is 0 to 3; and

p is 0 to 3;

provided that R is K when A is not J.

In the above definitions, the term "alkyl", used either alone or incompound words such as "alkylthio" or "haloalkyl", includes straightchain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or thedifferent butyl, pentyl, hexyl isomers.

Alkoxy includes methoxy, ethoxy, n-propyloxy, isopropyloxy and thedifferent butoxy or pentoxy isomers.

Alkenyl includes straight chain or branched alkenes, e.g., vinyl,1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyland hexenyl isomers.

Alkynyl includes straight chain or branched alkynes, e.g., ethynyl,1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynylisomers.

Alkylthio includes methylthio, ethylthio and the different propylthioand butylthio isomers.

Alkylsulfinyl, alkylsulfonyl, alkylamino, etc., are used analogously tothe above examples.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "halogen", either alone or in compound words such as"haloalkyl", means fluorine, chlorine, bromine or iodine. Further, whenused in compound words such as "haloalkyl" said alkyl may be partiallyor fully substituted with halogen atoms, which may be the same ordifferent. Examples of haloalkyl include CH₂ CH₂ F, CF₂ CF₂ and CH₂CHFCl. The terms "halocycloalkyl", "haloalkenyl" and "haloalkynyl" areused analogously to "haloalkyl". The term "compound(s)" employed hereinincludes all isomers and agriculturally suitable salts thereof.

The total number of carbon atoms in a substituent group is indicated bythe "C_(i) to C_(j) " prefix where i and j are numbers from 1 to 8. Forexample, C₁ to C₃ alkylsulfonyl would designate methylsulfonyl throughpropylsulfonyl; C₂ alkoxyalkoxy would designate OCH₂ OCH₃ ; C₄alkoxyalkoxy would designate the various isomers of an alkoxy groupsubstituted with a second alkoxy group containing a total of 4 carbonatoms, examples including OCH₂ OCH₂ CH₂ CH₃ and OCH₂ CH₂ OCH₂ CH₃ ; C₂cyanoalkyl would designate CH₂ CN and C₃ cyanoalkyl would designate CH₂CH₂ CN and CH(CN)CH₃ ; C₂ alkylcarbonyl would designate C(O)CH₃ and C₄alkylcarbonyl would include C(O)CH₂ CH₂ CH₃ and C(O)CH(CH₃)₂ ; and as afinal example, C₃ alkoxycarbonylalkyl would designate CH₂ CO₂ CH₃ and C₄alkoxycarbonylalkyl would include CH₂ CH₂ CO₂ CH₃, CH₂ CO₂ CH₂ CH₃ andCH(CH₃)CO₂ CH₃.

Preferred for higher insecticidal activity are compounds (Group A) ofFormula I wherein

R is ##STR10## and A is J.

Also preferred are the compounds (Group B) of preferred Group A wherein:

X is O;

Y is H, CH₃, SCH₃,SSCl₃, SC₆ H₅, 2-(NO₂)C₆ H₄ S, C(O)CH₃, C(O)H,C(O)CF₃, CO₂ CH₃, CO₂ CH₃, CO₂ C₂ H₅ or SX';

X' is X₁, X₂, X₃, X₄, X₅ or X₇ ;

R₆ and R₁₀ are independently selected from C₁ -C₆ alkyl, C₁ -C₆haloalkyl, C₅ -C₆ cycloalkyl, C₃ -C₈ alkoxycarbonylalkyl, phenyl, benzylor phenethyl each optionally substituted with W or R₆ and R₁₀ may betaken together as (CH₂)₄, (CH₂)₅ or (CH₂)₂ O(CH₂)₂ ;

R₈ and R₉ are independently selected from C₁ -C₃ alkyl and phenyl;

a is 2;

R₃ is C₁ to C₄ alkyl, C₁ to C₂ haloalkyl, C₂ to C₄ alkenyl, C₂ to C₄haloalkenyl, propargyl, phenyl, benzyl; or phenyl or benzyl substitutedwith one of F, Cl, Br, CF₃, OCF₂ H, OCF₃ or NO₂ ;

B is H, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₂ to C₆ alkoxyalkyl, C₂ toC₆ cyanoalkyl, C₃ to C₈ alkoxycarbonylalkyl, C₁ to C₆ alkenyl, C₁ to C₆alkynyl or C₂ to C₆ alkoxycarbonyl;

n is 0 to 2; and

m is 1 to 2.

Also preferred are the compounds (Group C) of preferred Group B wherein:

R₁ is halogen, CN, SCN, NO₂, R₃, OR₃, SR₃, S(O)₂ R₃, CO₂ R₃ or C(O)R₃,or when m is 2, R₁ can be taken together as --OCH₂ CH₂ O--, --CH₂C(CH₃)₂ O--, --OCF₂ CF₂ O-- or --CF₂ CF₂ O--;

R₂ is halogen, CN, SCN, NO₂, R₃, OR₃, SR₃, S(O)₂ R₃, OC(O)R₃, OS(O)₂ R₃,CO₂ R₃, C(O)R₃, C(O)NR₃ R₄, S(O)₂ NR₃ R₄ or NR₃ R₄ ;

R₃ is C₁ to C₄ alkyl, C₁ to C₂ haloalkyl, C₂ to C₄ alkenyl, C₂ to C₄haloalkenyl or propargyl;

R₄ is H or C₁ to C₂ alkyl;

W is halogen, CN, CO₂ CH₃, C(O)NHCH₃, C(O)N(CH₃)₂, NO₂, CH₃, CF₃, OCH₃,OCF₂ H, OCF₂ CF₂ H, SCH₃, SCF₂ H, SCF₂ CF₂ H or S(O)₂ CH₃ ;

B is H, C₁ to C₄ alkyl, C₁ to C₄ haloalkyl, or C₃ to C₄ alkenyl;

J is ##STR11## optionally substituted by one substituent selected fromW; and R₁₁ is H or C₁ to C₂ alkyl.

Also preferred are the compounds (Group D) of preferred Group C wherein:

Y is H, CH₃, C(O)CH₃, CO₂ CH₃ or SX';

X' is X₁, X₂, X₃ or X₅ ;

R₆ is C₁ -C₄ alkyl, CF₃, cyclohexyl, phenyl optionally substituted by W,or benzyl optionally substituted by W;

R₇ is F, C₁ -C₁₂ alkyl, C₁ -C₆ haloalkyl, phenyl or phenoxy eachoptionally substituted by W, C₁ -C₁₂ alkoxy, dimethylamino or C₁ -C₄alkoxy substituted with NO₂, C₂ -C₄ alkoxy or 1-6 halogens;

m is 1 or 2 and one substituent is in the 4-position of the phenyl ring;

n is 0, 1 or 2 and one substituent is in the 4-position of the phenylring;

R₁ is F, Cl, Br, CF₃, OCF₂ H, OCF₃, CN, or when m is 2, R₁ can be takentogether as --CH₂ C(CH₃)₂ O-- or --CF₂ CF₂ O--;

R₂ is F, Cl, Br, CN, NO₂, CF₃, CH₃, OCH₃, OCF₂ H, OCF₃, SCH₃, SCF₂ H,S(O)₂ CH₃ or N(CH₃)₂ ; and

B is H or CH₃.

Also preferred are the compounds (Group E) of Formula I wherein:

R is K and

A is C₁ to C₆ alkyl, phenyl, phenyl substituted by (R₅)_(p), CO₂ R₃,C(O)R₃, C(O)NR₃ R₄, C(S)NR₃ R₄, C(S)R₃ or C(S)SR₃.

Also preferred are the compounds (Group F) of Group E wherein:

X is O;

Y is H, CH₃, SCH₃, SCCl₃, SC₆ H₅, 2-(NO₂)C₆ H₄ S, C(O)CH₃, C(O)H,C(O)CF₃, CO₂ CH₃, CO₂ C₂ H₅ or SX';

X' is X₁, X₂, X₃, X₄, X₅ or X₇ ;

R₆ and R₁₀ are independently selected from C₁ -C₆ alkyl, C₁ -C₆haloalkyl, C₅ -C₆ cycloalkyl, C₃ -C₈ alkoxycarbonylalkyl, phenyl, benzylor phenethyl each optionally substituted with W or R₆ and R₁₀ may betaken together as (CH₂)₄, (CH₂)₅ or (CH₂)₂ O(CH₂)₂ ;

R₈ and R₉ are independently selected from C₁ -C₃ alkyl and phenyl;

a is 2;

R₃ is C₁ to C₄ alkyl, C₁ to C₂ haloalkyl, C₂ to C₄ alkenyl, C₂ to C₄haloalkenyl, propargyl, phenyl, benzyl, or phenyl or benzyl eachsubstituted with one of F, Cl, Br, CF₃, OCF₂ H, OCF₃ or NO₂ ;

m is 1 to 2; and

p is 0 to 2.

Also preferred are the compounds (Group G) of Group F wherein:

R₁ is halogen, CN, SCN, NO₂, R₃, OR₃, SR₃, S(O)₂ R₃, CO₂ R₃ or C(O)R₃,or when m is 2, R₁ can be taken together as --OCH₂ CH₂ O--, --CH₂C(CH₃)₂ O--, --OCF₂ CF₂ O-- or --CF₂ CF₂ O--;

R₃ is C₁ to C₄ alkyl, C₁ to C₂ haloalkyl, C₂ to C₄ alkenyl, C₂ to C₄haloalkenyl or propargyl;

R₄ is H or C₁ to C₂ alkyl;

R₅ is halogen, CN, SCN, NO₂, R₃, OR₃, SR₃, S(O)₂ R₃, OC(O)R₃, OS(O)₂ R₃,CO₂ R₃, C(O)R₃, C(O)NR₃ R₄, S(O)₂ NR₃ R₄ or NR₃ R₄ ;

W is halogen, CN, CO₂ CH₃, C(O)NHCH₃, C(O)N(CH₃)₂, NO₂, CH₃, CF₃, OCH₃,OCF₂ H, OCF₂ CF₂ H, SCH₃, SCF₂ H, SCF₂ CF₂ H or S(O)₂ CH₃ ;

A is C₁ to C₄ alkyl, phenyl, phenyl substituted with (R₅)_(p), CO₂ R₃,C(O)R₃, C(O)NR₃ R₄ or C(O)N(R₄)phenyl said phenyl optionally substitutedwith F, Cl, Br, CF₃, OCF₂ H, OCF₃ or NO₂ ;

B is H, C₁ to C₄ alkyl, C₁ to C₄ haloalkyl, or C₃ to C₄ alkenyl; and

K is ##STR12## substituted by at least one substituent selected from W;and R₁₁ is H or C₁ to C₂ alkyl.

Also preferred are the compounds (Group H) of Group G wherein:

Y is H, CH₃, C(O)CH₃, CO₂ CH₃ or SX';

X' is X₁, X₂, X₃ or X₅ ;

R₆ is C₁ -C₄ alkyl, CF₃, cyclohexyl, phenyl optionally substituted by W,or benzyl optionally substituted by W;

R₇ is F, C₁ -C₁₂ alkyl, C₁ -C₆ haloalkyl, phenyl or phenoxy optionallysubstituted by W, C₁ -C₁₂ alkoxy, dimethylamino or C₁ -C₄ alkoxysubstituted with NO₂, C₂ -C₄ alkoxy or 1-6 halogens;

R₁ is F, Cl, Br, CF₃, OCF₂ H, OCF₃, CN, or when m is 2, R₁ can be takentogether as --CH₂ C(CH₃)₂ O-- or --CF₂ CF₂ O--;

R₅ is F, Cl, Br, CN, NO₂, CF₃, CH₃, OCH₃, OCF₂ H, OCF₃, SCH₃, SCF₂ H,S(O)₂ CH₃, S(O)₂ CF₂ H, CO₂ CH₃, C(O)NHCH₃, C(O)N(CH₃)₂, S(O)₂ N(CH₃)₂or N(CH₃)₂ ;

A is phenyl or phenyl substituted with (R₅)_(p) ;

B is H or CH₃ ;

m is 1 or 2 and one substituent is in the 4-position of the phenyl ring;and

p is 0, 1 or 2 and one substituent is in the 3 or 4-position of thephenyl ring.

Also preferred are the compounds (Group I) of Group G wherein:

Y is H, CH₃, C(O)CH₃ or CO₂ CH₃ ;

X' is X₁, X₂ or X₅ ;

R₆ is C₁ -C₄ alkyl or phenyl optionally substituted with CH₃ or Cl;

R₇ is C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₁₂ alkoxy, dimethylamino orphenyl optionally substituted with CH₃ or Cl;

R₁ is F, Cl, Br, CF₃, OCF₂ H, OCF₃ or CN;

A is CO₂ CH₃, CO₂ C₂ H₅, C(O)NHCH₃ or C(O)N(CH₃)₂ ;

B is CH₃ ; and

m is 1 or 2 and one substituent is in the 4-position of the phenyl ring.

Specifically preferred compounds are:

1-(4-chlorophenyl)-5-(2-furanyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide,

1-(5-chloro-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide,

1-(5-bromo-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide,

1-(4-chlorophenyl)-5-(5-chloro-2-pyridinyl)-4,5-dihydro-5-methyl-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide,and

1-(4-chlorophenyl)-5-(5-chloro-2-thienyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide.

DETAILS OF THE INVENTION

Compounds of Formula I can be obtained by the reaction of activatedcarbonyl or thiocarbonyl compounds of Formula II with substitutedanilines in the presence or absence of an acid acceptor or suitablecondensing agent. Methods for performing this transformation are wellknown in the art; see, Zabicky, "The Chemistry of the Amides",Interscience, 1970.

One particularly useful method involves the chlorination of an acidderivative (II, X₁ =OH) with thionyl chloride or another chlorinatingagent followed by treatment with an aniline (III) in the presence of anacid acceptor such as an amine base, preferably triethylamine. Suitablesolvents for the chlorination reaction are inert to hydrogen chlorideand include benzene, toluene, and dichloromethane. Preferredtemperatures for this process are from 20° to 100° C. with temperaturesbetween 20° and 80° C. being particularly preferred. The latter reactioncan be carried out in many different inert solvents such asdialkylethers, chlorinated hydrocarbons, and aromatic hydrocarbons.While temperatures at or below 25° C. are preferred, higher temperaturescan also be employed. These reactions are normally run at atmosphericpressure, but can also be carried out at elevated pressures. ##STR13##

Esters of Formula II (X₁ =C₁ to C₆ alkoxy) can be converted directly tocompounds of Formula I in several ways. In the presence of Lewis acidssuch as AlMe₃, anilines react readily with esters of Formula II. Thereaction is best carried out at room temperature to 120° C. Suitablesolvents include dichloromethane, 1,2-dichloroethane, and toluene. Themethod described by Weinreb et al., Organic Synthesis, 59, 49, (1982),proceeds best with esters of lower alcohols such as methanol or ethanol.

Acids of Formula II (X₁ =OH) can be converted directly to compounds ofFormula I by use of coupling agents known in the peptide art inconjunction with anilines. Coupling agents includedicyclohexylcarbodiimide (DCC), N-hydroxysuccinimide,2-chloro-N-methylpyridinium iodide, carbonyl diimidazole, or otheragents capable of activating an acid function or acting as a dehydratingagent. These and other methods are described in Gross et al., "ThePeptides," 3 Vols., Academic Press, New York, 1979 to 1981.

Compounds of Formula I can also be obtained from the cyclization ofappropriate phenyl or heteroaryl hydrazines (V) with keto-acidderivatives (IV). It will be appreciated by those skilled in the artthat this process applies equally to acids, esters, and anilides andfurther that the interconversion of these groups as discussed in thesequence (II→I) can be carried out after the cyclization reaction. Theconditions for these reactions are well known in the art and describedby Hill et al., Trans. Illinois Acad. Sci., 33 (1940), 112 and byVaughan, J. Org. Chem., 20 (1955), 1619. The cyclization reaction isbest carried out on an unsaturated keto-acid derivative (IV) inrefluxing alcoholic media, in refluxing lower carboxylic acids, or inpolar aprotic solvents such as dimethylformamide or dimethyl sulfoxide.Ethanol containing acetic acid or acetic acid alone are the preferredsolvents although other protic or aprotic solvents and mixtures are alsoapplicable. In some cases, phenyl hydrazones can be isolated prior tofinal cyclization and these can be refluxed further in order to completethe cyclization. While the unsaturated acid derivatives (IV) arepreferred, saturated compounds with a reactive group such as a halogenbeta to the carbonyl can be employed in certain instances. The mostPreferred Z substituents for the cyclization are the acids and anilides.##STR14##

Many of the required aryl and heteroaryl hydrazines (V) are availablefrom commercial sources. The synthesis of these substrates is well knownin the art; see Enders in Houben-Weyl's "Methoden der OrganischenChemie", Vol. 10/2; 177 to 348, Georg Thieme Verlag, Stuttgart, 1967.

Compounds of Formula I and intermediates of Formula II can also beobtained by the dipolar cycloaddition reaction of nitrile-imines,generated from substituted phenylhydrazones of Formula VI, withappropriately substituted alkenes. The presence of an acid acceptor(generally an amine base, for example, triethylamine) is necessary forthe formation of the nitrile-imine. In a typical reaction, the alkene isused in a two- to five-fold molar excess and the amine base in a three-to five-fold excess based on the hydrazone (VI). Suitable solventsinclude but are not restricted to benzene, toluene, 1,2-dichloroethane,chloroform, and tetrahydrofuran. The reaction can be carried out attemperatures ranging from 20° to 120° C. with the relative reactivity ofthe alkene (VII) governing the required temperature for a given example.The required hydrazones (VI) for the synthesis of compounds of Formula Iand II can be prepared by methods known in the art or by modificationsthereof; see, e.g., Shawali et al., Tetrahedron, 20 (1971), 2517.

The alkenes such as (VII) used in cycloaddition reactions are generallyavailable commercially. Other alkenes can be synthesized by many methodssuch as those described in March, "Advanced Organic Chemistry", 3rdEdition, Wiley, New York, pages 1149 to 1151. ##STR15## Nitrile-iminesmay also be generated by other methods which may be better suited forbasic nitrogen containing heterocycles such as pyridine. The thermal orphotolytic decomposition of 2,5-disubstituted tetrazoles producesnitrile-imines. Tetrazoles (VIII) suitable for use in the presentinvention may be obtained by the general route of Lippmann et al.(Monatshefte fur Chemie, 106, 1975, 437.). The thermolysis of tetrazolesgenerally requires high temperatures from 200° to 400° C. Photolysiswith high intensity lamps can be performed on these compounds at roomtemperature to 120° C. Suitable solvents include benzene, dioxane, andtoluene. The reaction is best performed in dilute solutions in thepresence of one or more equivalents of an alkene. Use of CuSO₄ solutionor a pyrex filter in the photolysis apparatus is preferred. ##STR16##The photolysis of syndnones is another method of nitrile-iminegeneration. Irradiation of a dilute solution of the sydnone (IX) (about0.05M) in the presence of an excess of the alkene at or near roomtemperature gives the compounds of the present invention. Sydnones (IX)of the desired structures can be obtained by the metallation of thesydnones (X) and subsequent reaction with phenylisocyanates,chloroformates, or carbon dioxide. Metallation and trapping of thesydnones is best performed at temperatures lower than -20° C. Typicalsolvents used are diethyl ether and tetrahydrofuran. Metallation can beaccomplished with n-butyl lithium and other alkyl lithium bases.##STR17##

Certain reactions can be used to convert various functional groups intoheterocycles on already formed pyrazolines (I or II). One convenientmethod involves taking an aldehyde (I or II A=CHO) and treating it withp-toluene sulfonyl isocyanide (TOSMIC) and an acid acceptor. Theresulting product is an oxazole (I or II A=oxazole). The reaction iscarried out in polar organic solvents such as alcohols. The preferredbases are inorganic salts such as potassium carbonate, sodium carbonateor potassium bicarbonate. ##STR18##

Some compounds of Formula I (Y=H) can be converted to other compounds ofFormula I by alkylation, acylation, and sulphenylation reactions (Y=H).Reaction of compounds of Formula I in the presence of an acid acceptorwith electrophilic agents (Y=leaving group) results in substitution onnitrogen. Strong bases such as sodium hydride, potassium t-butoxide,potassium hydride, and other bases known in the art to deprotonateamides are preferred in the process. Suitable electrophiles include, butare not restricted to alkyl halides, acyl halides, acid anhydrides,carbonates, chloroformates, disulphides, and sulphenyl halides. Thisreaction is normally run in the temperature range of 0° to 25° C., butcan be run at temperatures up to 120° C. if unreactive electrophiles areused. Solvents not deprotonated under the reactions conditions such astetrahydrofuran, dimethylformamide, dimethoxyethane, and diethyl etherare preferred.

Compounds of Formula I (X=O) can be converted to compounds of Formula I(X=S) by means of thiating agents. Conversion of amides to thioamides iswell known in the art. Phosphorous pentasulfide either alone or incombination with organic or inorganic bases is a preferred reagent toeffect this conversion. When phosphorous pentasulfide is used alone,organic bases such as pyridine are the preferred solvents. When it isused in conjunction with inorganic bases such as sodium bicarbonate, thepreferred solvents are ethers such as diglyme. Temperatures between 20°to 160° C. can be employed successfully with temperatures between 90° to120° C. preferred. These and other means to convert amides to thioamidesare described by Lapucha, Synthesis (1987), 256.

It will be appreciated by those skilled in the art that, regardless ofthe method of synthesis, compounds of Formula II can be converted tocompounds of the instant invention by the methods described above. Manyfunctional group transformations known to those skilled in the art canbe employed to convert compounds of Formula I to new compounds ofFormula I and that this will overcome any incompatibility of certainsuch groups with reagents and conditions disclosed above with respect totypical reaction mechanisms.

The following examples illustrate the invention.

EXAMPLE 1 Methyl chloro[2-(4-chlorophenyl)hydrazono]acetate

To a suspension of 4-chloroaniline (41.75 g) in 6N HCl (170 ml) cooledto 0° C. was slowly added a solution of sodium nitrite (23.9 g) inwater. The resulting cold solution was added gradually by means of aninsulated dropping funnel to a suspension of 2-chloroacetoacetate (40ml) and sodium acetate (85.2 g) in ethanol (450 ml). The reactionmixture was vigorously stirred and cooled to keep the temperature below10° C. during the addition. The reaction was then allowed to warm toroom temperature. The precipitated product was filtered, washed withwater and air dried. Recrystallization from benzene gave the product in2 crops (56.0 g). m.p.: 149° to 150° C., NMR (CDCl₃); 8.3 (m, HH); 7.3(m, 2H); 7.1 (m, 2H); 3.9 (s, 3H, CH₃).

EXAMPLE 2 Methyl1-(4-chlorophenyl)-5-(2-furanyl)-4,5-dihydro-1H-pyrazole- 3-carboxylate

The compound of Example 1 (2.0 g) was suspended in benzene (20 ml) andheated to reflux in the presence of 2-vinylfuran (2.5 ml). Triethylaminewas added and the mixture was allowed to reflux for 1 hour longer. Themixture was partitioned between water and ethyl acetate. The ethylacetate layer was dried over magnesium sulfate and concentrated.Chromatography on silica gel (5:1 hexanes/ethyl acetate) gave the titlecompound (1.8 g). NMR (CDCl₃) 7.3 to 6.9 (m, Ar-H, 5H); 6.2 (m, Furan-H,2H); 5.5 (dd, CH, 1H); 3.9 (s, OCH₃, 3H); 3.6 (m, CH, 1H); 3.4 (m, CH₃,1H).

EXAMPLE 31-(4-Chlorophenyl)-5-(2-furanyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide

The compound of Example 2 (1.4 g) was heated to reflux in methanol (20ml) with 50% sodium hydroxide (1.0 ml) for 1 hour. The mixture wascooled and acidified with 1N HCl. Extraction with ethyl acetate, drying,and evaporation gave the acid. The acid was suspended in benzene (10 ml)and heated to reflux with thionyl chloride (1.5 ml). After heating for 2hours, the mixture was evaporated and azeotroped with toluene (10 ml).The residue was dissolved in tetrahydrofuran (20 ml) and divided in two.One aliquot was added to a stirred mixture of 4-amino benzotrifluoride(0.3 ml) and triethylamine (0.5 ml). After 30 minutes of stirring, themixture was diluted with 1N HCl (50 ml) and ethyl acetate (50 ml). Theethyl acetate layer was washed with sodium bicarbonate solution (50 ml)and with brine (50 ml). Drying over magnesium sulfate and evaporationprovided the crude product. Recrystallization from methylenechloride/methanol gave the title compound (0.54 g). m.p.: 167° to 171°C. NMR (CDCl₃) 8.6 (Br, NH); 7.7-7.1 (m, ArH, 9H); 6.3 (m, furan-H, 2H);5.5 (m, CH, 1H); 3.7 (m, CH, 1H); 3.5 (m, CH, 1H).

EXAMPLE 41-(6-Chloro-3-pyridazinyl)-5-(4-fluorophenyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide

Part A: To make potassium 4-(4-fluorophenyl)-2-oxo-3-butenoate, asolution of pyruvic acid and p-fluorobenzaldehyde (24.8 g) in methanol(20 ml) were cooled to 15° C. and treated with a solution of potassiumhydroxide (16.8 g) in (50 ml) methanol. After 2/3 of the addition wascomplete, the cooling bath was removed and the temperature was allowedto rise to 40° C. A yellow precipitate appeared and was filtered afterstanding overnight. The solid was washed well with methanol and ether.The compound (34.5 g) was used without further purification in Part B.

Part B: The compound of Part A was converted to the correspondingcarboxylic acid by the general method of Stecher (J. Am. Chem. Soc.,1952, 74, 4392). The free acid (from 8 g of potassium salt) wassuspended in benzene (150 ml) and thionyl chloride (6 ml). The mixturewas heated to reflux for 10 minutes with dimethylformamide (4 drops) andallowed to cool to room temperature. After stirring for 4 hours themixture was concentrated under reduced pressure. The residue wasdissolved in tetrahydrofuran (100 ml) and then added dropwise withcooling to a solution of triethylamine (10 ml) and4-aminobenzotrifluoride (6.5 g). The mixture was stirred for 30 minutesand partitioned between ethyl acetate and 1N HCl. The organic layer waswashed with saturated sodium bicarbonate, dried, and evaporated. Thesolid residue was recrystallized from butyl chloride to give4-(4-fluorophenyl)-2-oxo-N-[4-(trifluoromethyl)phenyl]-3-butenamide (5.2g) m.p.: 200° to 201° C.; NMR (CDCl₃ ); 9.2 (Br, NH); 8.0 to 7.1 (m, Arand CH₂, 10H).

Part C: The compound of Part B (0.9 g) was dissolved indimethylformamide (8 ml) and treated with 6-chloro-3-hydrazinopyridazine(0.3 g) and then heated for 2 hours at reflux. The solvent wasevaporated under reduced pressure. The residue was chromatographed onsilica gel (hexane/ethyl acetate (3:1)). The main fraction wascrystallized by addition of hexane to give the title compound (0.53 g).m.p.: 200° to 202° C.; NMR (CDCl₃); 8.6 (br, NH); 7.8 to 6.9 (m, ArH,10H); 5.9 (dd, CH, 1H); 3.85 (dd, 1H, CH); 3.3 (dd, CH, 1H).

EXAMPLE 51-(5-Chloro-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro-N-(4-trifluoromethyl)phenyl-1H-pyrazole-3-carboxamide

The procedure for Example 4 was used and 5-chloro-2-pyridyl hydrazine(0.34 g) was substituted in Part C to yield the title compound (0.49 g).m.p.: 175 to 177 (MeOH); NMR (CDCl₃); 8.6 (NH), 8.0 to 7.0 (m, ArH); 5.8(m, CH); 3.8 (m, CH); 3.2 (m, CH).

EXAMPLE 6 1H-Pyrazole-3-carboxamide,1-(4-fluorophenyl)-4,5-dihydro-5-methyl-5-(5-oxazolyl)-N-((4-trifluoromethyl)phenyl))

The starting material, 1H-pyrazole-3-carboxamide,1-(4-fluorophenyl)-5-formyl-4,5-dihydro-5-methyl-N-((4-(trifluoromethyl)phenyl)),was synthesized by the general procedures for Examples 1 to 3 usingp-fluoroaniline instead of p-chloroaniline in Example 1 and methacroleinin place of 2-vinylfuran in Example 2. The starting material (0.5 g) andp-toluenesulfonylisocyanide (0.24 g) were suspended in methanol (5 ml)and stirred at room temperature for 4 hours. The mixture was poured intowater (100 ml) and extracted with ethyl acetate (3×100 ml). The organiclayer was dried and evaporated. The residue was chromatographed onsilica gel (hexanes/ethyl acetate 1:1) to give the title compound as asolid (0.27 g); m.p.=142° to 145° C. NMR (CDCl₃) 8.2-6.9 (m, ArH and NH,10H); 3.6 (m, 2H, CH₂); 1.69 (s, CH₃, 3H).

Generic structures for the compound species listed in Tables 1 to 5 areas follows: ##STR19##

                  TABLE 1                                                         ______________________________________                                        R.sub.1 R.sub.2   J             (m.p. °C.)                             ______________________________________                                        4-CF.sub.3                                                                            4-Cl      2-pyridyl       174 to 174.5                                4-CF.sub.3                                                                            4-F       2-pyridyl                                                   4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-pyridyl                                                   4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-pyridyl                                                   4-CF.sub.3                                                                            4-CN      2-pyridyl                                                   4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-pyridyl                                                   4-CF.sub.3                                                                            4-Cl      3-pyridyl                                                   4-CF.sub.3                                                                            4-F       3-pyridyl                                                   4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           3-pyridyl                                                   4-CF.sub.3                                                                            4-CF.sub.3                                                                              3-pyridyl                                                   4-CF.sub.3                                                                            4-CN      3-pyridyl                                                   4-CF.sub.3                                                                            4-OCF.sub.3                                                                             3-pyridyl                                                   4-CF.sub.3                                                                            4-Cl      4-pyridyl                                                   4-CF.sub.3                                                                            4-F       4-pyridyl                                                   4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           4-pyridyl                                                   4-CF.sub.3                                                                            4-CF.sub.3                                                                              4-pyridyl                                                   4-CF.sub.3                                                                            4-CN      4-pyridyl                                                   4-CF.sub.3                                                                            4-OCF.sub.3                                                                             4-pyridyl                                                   4-CF.sub.3                                                                            4-Cl      5-Cl-pyrid-2-yl                                                                             175 to 177                                    4-CF.sub.3                                                                            4-F       5-Cl-pyrid-2-yl                                             4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-Cl-pyrid-2-yl                                             4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-Cl-pyrid-2-yl                                             4-CF.sub.3                                                                            4-CN      5-Cl-pyrid-2-yl                                             4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-Cl-pyrid-2-yl                                             4-CF.sub.3                                                                            4-Cl      6-Cl-pyrid-3-yl                                             4-CF.sub.3                                                                            4-F       6-Cl-pyrid-3-yl                                             4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           6-Cl-pyrid-3-yl                                             4-CF.sub.3                                                                            4-CF.sub.3                                                                              6-Cl-pyrid-3-yl                                             4-CF.sub.3                                                                            4-CN      6-Cl-pyrid-3-yl                                             4-CF.sub.3                                                                            4-OCF.sub.3                                                                             6-Cl-pyrid-3-yl                                             4-CF.sub.3                                                                            4-Cl      6-F-pyrid-3-yl                                              4-CF.sub.3                                                                            4-F       6-F-pyrid-3-yl                                              4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           6-F-pyrid-3-yl                                              4-CF.sub.3                                                                            4-CF.sub.3                                                                              6-F-pyrid-3-yl                                              4-CF.sub.3                                                                            4-CN      6-F-pyrid-3-yl                                              4-CF.sub.3                                                                            4-OCF.sub.3                                                                             6-F-pyrid-3-yl                                              4-CF.sub.3                                                                            4-Cl      2-thienyl                                                   4-CF.sub.3                                                                            4-F       2-thienyl                                                   4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-thienyl                                                   4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-thienyl                                                   4-CF.sub.3                                                                            4-CN      2-thienyl                                                   4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-thienyl                                                   4-CF.sub.3                                                                            4-Cl      3-thienyl     204 to 206                                    4-CF.sub.3                                                                            4-F       3-thienyl                                                   4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           3-thienyl                                                   4-CF.sub.3                                                                            4-CF.sub.3                                                                              3-thienyl                                                   4-CF.sub.3                                                                            4-CN      3-thienyl                                                   4-CF.sub.3                                                                            4-OCF.sub.3                                                                             3-thienyl                                                   4-CF.sub.3                                                                            4-Cl      5-Cl-thien-2-yl                                             4-CF.sub.3                                                                            4-F       5-Cl-thien-2-yl                                             4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-Cl-thien-2-yl                                             4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-Cl-thien-2-yl                                             4-CF.sub.3                                                                            4-CN      5-Cl-thien-2-yl                                             4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-Cl-thien-2-yl                                             4-CF.sub.3                                                                            4-Cl      5-Cl-thien-3-yl                                             4-CF.sub.3                                                                            4-F       5-Cl-thien-3-yl                                             4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-Cl-thien-3-yl                                             4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-Cl-thien-3-yl                                             4-CF.sub.3                                                                            4-CN      5-Cl-thien-3-yl                                             4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-Cl-thien-3-yl                                             4-CF.sub.3                                                                            4-Cl      5-F-thien-3-yl                                              4-CF.sub.3                                                                            4-F       5-F-thien-3-yl                                              4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-F-thien-3-yl                                              4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-F-thien-3-yl                                              4-CF.sub.3                                                                            4-CN      5-F-thien-3-yl                                              4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-F-thien-3-yl                                              4-CF.sub.3                                                                            4-Cl      2-furyl       167 to 171                                    4-CF.sub.3                                                                            4-F       2-furyl                                                     4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-furyl                                                     4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-furyl                                                     4-CF.sub.3                                                                            4-CN      2-furyl                                                     4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-furyl                                                     4-CF.sub.3                                                                            4-Cl      3-furyl                                                     4-CF.sub.3                                                                            4-F       3-furyl                                                     4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           3-furyl                                                     4-CF.sub.3                                                                            4-CF.sub.3                                                                              3-furyl                                                     4-CF.sub.3                                                                            4-CN      3-furyl                                                     4-CF.sub.3                                                                            4-OCF.sub.3                                                                             3-furyl                                                     4-CF.sub.3                                                                            4-Cl      5-Cl-fur-2-yl                                               4-CF.sub.3                                                                            4-F       5-Cl-fur-2-yl                                               4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-Cl-fur-2-yl                                               4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-Cl-fur-2-yl                                               4-CF.sub.3                                                                            4-CN      5-Cl-fur-2-yl                                               4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-Cl-fur-2-yl                                               4-CF.sub.3                                                                            4-Cl      5-Cl-fur-3-yl                                               4-CF.sub.3                                                                            4-F       5-Cl-fur-3-yl                                               4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-Cl-fur-3-yl                                               4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-Cl-fur-3-yl                                               4-CF.sub.3                                                                            4-CN      5-Cl-fur-3-yl                                               4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-Cl-fur-3-yl                                               4-CF.sub.3                                                                            4-Cl      2-pyrimidyl                                                 4-CF.sub.3                                                                            4-F       2-pyrimidyl                                                 4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-pyrimidyl                                                 4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-pyrimidyl                                                 4-CF.sub.3                                                                            4-CN      2-pyrimidyl                                                 4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-pyrimidyl                                                 4-CF.sub.3                                                                            4-Cl      4-pyrimidyl                                                 4-CF.sub.3                                                                            4-F       4-pyrimidyl                                                 4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           4-pyrimidyl                                                 4-CF.sub.3                                                                            4-CF.sub. 3                                                                             4-pyrimidyl                                                 4-CF.sub.3                                                                            4-CN      4-pyrimidyl                                                 4-CF.sub.3                                                                            4-OCF.sub.3                                                                             4-pyrimidyl                                                 4-CF.sub.3                                                                            4-Cl      5-pyrimidyl                                                 4-CF.sub.3                                                                            4-F       5-pyrimidyl                                                 4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-pyrimidyl                                                 4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-pyrimidyl                                                 4-CF.sub.3                                                                            4-CN      5-pyrimidyl                                                 4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-pyrimidyl                                                 4-CF.sub.3                                                                            4-Cl      2-Cl-pyrimid-5-yl                                           4-CF.sub.3                                                                            4-F       2-Cl-pyrimid-5-yl                                           4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-Cl-pyrimid-5-yl                                           4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-Cl-pyrimid-5-yl                                           4-CF.sub.3                                                                            4-CN      2-Cl-pyrimid-5-yl                                           4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-Cl-pyrimid-5-yl                                           4-CF.sub.3                                                                            4-Cl      2-pyrazinyl                                                 4-CF.sub.3                                                                            4-F       2-pyrazinyl                                                 4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-pyrazinyl                                                 4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-pyrazinyl                                                 4-CF.sub.3                                                                            4-CN      2-pyrazinyl                                                 4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-pyrazinyl                                                 4-CF.sub.3                                                                            4-Cl      5-Cl-pyrazin-2-yl                                           4-CF.sub.3                                                                            4-F       5-Cl-pyrazin-2-yl                                           4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           5-Cl-pyrazin-2-yl                                           4-CF.sub.3                                                                            4-CF.sub.3                                                                              5-Cl-pyrazin-2-yl                                           4-CF.sub.3                                                                            4-CN      5-Cl-pyrazin-2-yl                                           4-CF.sub.3                                                                            4-OCF.sub.3                                                                             5-Cl-pyrazin-2-yl                                           4-CF.sub.3                                                                            4-Cl      2-pyridazinyl                                               4-CF.sub.3                                                                            4-F       2-pyridazinyl                                               4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-pyridazinyl                                               4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-pyridazinyl                                               4-CF.sub.3                                                                            4-CN      2-pyridazinyl                                               4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-pyridazinyl                                               4-CF.sub.3                                                                            4-Cl      2-thiazolyl                                                 4-CF.sub.3                                                                            4-F       2-thiazolyl                                                 4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-thiazolyl                                                 4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-thiazolyl                                                 4-CF.sub.3                                                                            4-CN      2-thiazolyl                                                 4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-thiazolyl                                                 4-CF.sub.3                                                                            4-Cl      2-oxazolyl                                                  4-CF.sub.3                                                                            4-F       2-oxazolyl                                                  4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           2-oxazolyl                                                  4-CF.sub.3                                                                            4-CF.sub.3                                                                              2-oxazolyl                                                  4-CF.sub.3                                                                            4-CN      2-oxazolyl                                                  4-CF.sub.3                                                                            4-OCF.sub.3                                                                             2-oxazolyl                                                  4-CF.sub.3                                                                            4-Cl      1-Me-imidazol-2-yl                                          4-CF.sub.3                                                                            4-F       1-Me-imidazol-2-yl                                          4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           1-Me-imidazol-2-yl                                          4-CF.sub.3                                                                            4-CF.sub.3                                                                              1-Me-imidazol-2-yl                                          4-CF.sub.3                                                                            4-CN      1-Me-imidazol-2-yl                                          4-CF.sub.3                                                                            4-OCF.sub.3                                                                             1-Me-imidazol-2-yl                                          4-CF.sub.3                                                                            4-Cl      1-Me-imidazol-4-yl                                          4-CF.sub.3                                                                            4-F       1-Me-imidazol-4-yl                                          4-CF.sub.3                                                                            4-OCF.sub.2 H                                                                           1-Me-imidazol-4-yl                                          4-CF.sub.3                                                                            4-CF.sub.3                                                                              1-Me-imidazol-4-yl                                          4-CF.sub.3                                                                            4-CN      1-Me-imidazol-4-yl                                          4-CF.sub.3                                                                            4-OCF.sub.3                                                                             1-Me-imidazol-4-yl                                          4-OCF.sub.3                                                                           4-Cl      2-pyridyl                                                   4-OCF.sub.3                                                                           4-F       2-pyridyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           2-pyridyl                                                   4-OCF.sub.3                                                                           4-CF.sub.3                                                                              2-pyridyl                                                   4-OCF.sub.3                                                                           4-CN      2-pyridyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             2-pyridyl                                                   4-OCF.sub.3                                                                           4-Cl      3-pyridyl                                                   4-OCF.sub.3                                                                           4-F       3-pyridyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           3-pyridyl                                                   4-OCF.sub.3                                                                           4-CF.sub.3                                                                              3-pyridyl                                                   4-OCF.sub.3                                                                           4-CN      3-pyridyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             3-pyridyl                                                   4-OCF.sub.3                                                                           4-Cl      4-pyridyl                                                   4-OCF.sub.3                                                                           4-F       4-pyridyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           4-pyridyl                                                   4-OCF.sub.3                                                                           4-CF.sub.3                                                                              4-pyridyl                                                   4-OCF.sub.3                                                                           4-CN      4-pyridyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             4-pyridyl                                                   4-OCF.sub.3                                                                           4-Cl      5-Cl-pyrid-2-yl                                             4-OCF.sub.3                                                                           4-F       5-Cl-pyrid-2-yl                                             4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           5-Cl-pyrid-2-yl                                             4-OCF.sub.3                                                                           4-CF.sub.3                                                                              5-Cl-pyrid-2-yl                                             4-OCF.sub.3                                                                           4-CN      5-Cl-pyrid-2-yl                                             4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             5-Cl-pyrid-2-yl                                             4-OCF.sub.3                                                                           4-Cl      2-thienyl                                                   4-OCF.sub.3                                                                           4-F       2-thienyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           2-thienyl                                                   4-OCF.sub.3                                                                           4-CF.sub.3                                                                              2-thienyl                                                   4-OCF.sub.3                                                                           4-CN      2-thienyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             2-thienyl                                                   4-OCF.sub.3                                                                           4-Cl      3-thienyl                                                   4-OCF.sub.3                                                                           4-F       3-thienyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           3-thienyl                                                   4-OCF.sub.3                                                                           4-CF.sub.3                                                                              3-thienyl                                                   4-OCF.sub.3                                                                           4-CN      3-thienyl                                                   4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             3-thienyl                                                   4-OCF.sub.3                                                                           4-Cl      5-Cl-thien-2-yl                                             4-OCF.sub.3                                                                           4-F       5-Cl-thien-2-yl                                             4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           5-Cl-thien-2-yl                                             4-OCF.sub.3                                                                           4-CF.sub.3                                                                              5-Cl-thien-2-yl                                             4-OCF.sub.3                                                                           4-CN      5-Cl-thien-2-yl                                             4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             5-Cl-thien-2-yl                                             4-OCF.sub.3                                                                           4-Cl      5-Cl-thien-3-yl                                             4-OCF.sub.3                                                                           4-F       5-Cl-thien-3-yl                                             4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           5-Cl-thien-3-yl                                             4-OCF.sub.3                                                                           4-CF.sub.3                                                                              5-Cl-thien-3-yl                                             4-OCF.sub.3                                                                           4-CN      5-Cl-thien-3-yl                                             4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             5-Cl-thien-3-yl                                             4-OCF.sub.3                                                                           4-Cl      2-furyl                                                     4-OCF.sub.3                                                                           4-F       2-furyl                                                     4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           2-furyl                                                     4-OCF.sub.3                                                                           4-CF.sub.3                                                                              2-furyl                                                     4-OCF.sub.3                                                                           4-CN      2-furyl                                                     4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             2-furyl                                                     4-OCF.sub.3                                                                           4-Cl      3-furyl                                                     4-OCF.sub.3                                                                           4-F       3-furyl                                                     4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           3-furyl                                                     4-OCF.sub.3                                                                           4-CF.sub.3                                                                              3-furyl                                                     4-OCF.sub.3                                                                           4-CN      3-furyl                                                     4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             3-furyl                                                     4-OCF.sub.3                                                                           4-Cl      5-pyrimidyl                                                 4-OCF.sub.3                                                                           4-F       5-pyrimidyl                                                 4-OCF.sub.3                                                                           4-OCF.sub.2 H                                                                           5-pyrimidyl                                                 4-OCF.sub.3                                                                           4-CF.sub.3                                                                              5-pyrimidyl                                                 4-OCF.sub.3                                                                           4-CN      5-pyrimidyl                                                 4-OCF.sub.3                                                                           4-OCF.sub.3                                                                             5-pyrimidyl                                                 4-Cl    4-Cl      2-pyridyl                                                   4-Cl    4-F       2-pyridyl                                                   4-Cl    4-OCF.sub.2 H                                                                           2-pyridyl                                                   4-Cl    4-CF.sub.3                                                                              2-pyridyl                                                   4-Cl    4-CN      2-pyridyl                                                   4-Cl    4-OCF.sub.3                                                                             2-pyridyl                                                   4-Cl    4-Cl      4-pyridyl                                                   4-Cl    4-F       4-pyridyl                                                   4-Cl    4-OCF.sub.2 H                                                                           4-pyridyl                                                   4-Cl    4-CF.sub.3                                                                              4-pyridyl                                                   4-Cl    4-CN      4-pyridyl                                                   4-Cl    4-OCF.sub.3                                                                             4-pyridyl                                                   4-Cl    4-Cl      2-thienyl                                                   4-Cl    4-F       2-thienyl                                                   4-Cl    4-OCF.sub.2 H                                                                           2-thienyl                                                   4-Cl    4-CF.sub.3                                                                              2-thienyl                                                   4-Cl    4-CN      2-thienyl                                                   4-Cl    4-OCF.sub.3                                                                             2-thienyl                                                   4-Cl    4-Cl      3-thienyl     215 to 217                                    4-Cl    4-F       3-thienyl                                                   4-Cl    4-OCF.sub.2 H                                                                           3-thienyl                                                   4-Cl    4-CF.sub.3                                                                              3-thienyl                                                   4-Cl    4-CN      3-thienyl                                                   4-Cl    4-OCF.sub.3                                                                             3-thienyl                                                   4-Cl    4-Cl      5-Cl-thien-2-yl                                             4-Cl    4-F       5-Cl-thien-2-yl                                             4-Cl    4-OCF.sub.2 H                                                                           5-Cl-thien-2-yl                                             4-Cl    4-CF.sub.3                                                                              5-Cl-thien-2-yl                                             4-Cl    4-CN      5-Cl-thien-2-yl                                             4-Cl    4-OCF.sub.3                                                                             5-Cl-thien-2-yl                                             4-Cl    4-Cl      2-furyl         187 to 188.5                                4-Cl    4-F       2-furyl                                                     4-Cl    4-OCF.sub.2 H                                                                           2-furyl                                                     4-Cl    4-CF.sub.3                                                                              2-furyl                                                     4-Cl    4-CN      2-furyl                                                     4-Cl    4-OCF.sub.3                                                                             2-furyl                                                     4-Cl    4-Cl      3-furyl                                                     4-Cl    4-F       3-furyl                                                     4-Cl    4-OCF.sub.2 H                                                                           3-furyl                                                     4-Cl    4-CF.sub.3                                                                              3-furyl                                                     4-Cl    4-CN      3-furyl                                                     4-Cl    4-OCF.sub.3                                                                             3-furyl                                                     4-Cl    4-Cl      5-pyrimidyl                                                 4-Cl    4-F       5-pyrimidyl                                                 4-Cl    4-OCF.sub.2 H                                                                           5-pyrimidyl                                                 4-Cl    4-CF.sub.3                                                                              5-pyrimidyl                                                 4-Cl    4-CN      5-pyrimidyl                                                 4-Cl    4-OCF.sub.3                                                                             5-pyrimidyl                                                 4-Br    4-Cl      2-pyridyl                                                   4-Br    4-F       2-pyridyl                                                   4-Br    4-OCF.sub.2 H                                                                           2-pyridyl                                                   4-Br    4-CF.sub.3                                                                              2-pyridyl                                                   4-Br    4-CN      2-pyridyl                                                   4-Br    4-OCF.sub.3                                                                             2-pyridyl                                                   4-Br    4-Cl      4-pyridyl                                                   4-Br    4-F       4-pyridyl                                                   4-Br    4-OCF.sub.2 H                                                                           4-pyridyl                                                   4-Br    4-CF.sub.3                                                                              4-pyridyl                                                   4-Br    4-CN      4-pyridyl                                                   4-Br    4-OCF.sub.3                                                                             4-pyridyl                                                   4-Br    4-Cl      2-thienyl                                                   4-Br    4-F       2-thienyl                                                   4-Br    4-OCF.sub.2 H                                                                           2-thienyl                                                   4-Br    4-CF.sub.3                                                                              2-thienyl                                                   4-Br    4-CN      2-thienyl                                                   4-Br    4-OCF.sub.3                                                                             2-thienyl                                                   4-Br    4-Cl      3-thienyl     220 to 222                                    4-Br    4-F       3-thienyl                                                   4-Br    4-OCF.sub.2 H                                                                           3-thienyl                                                   4-Br    4-CF.sub.3                                                                              3-thienyl                                                   4-Br    4-CN      3-thienyl                                                   4-Br    4-OCF.sub.3                                                                             3-thienyl                                                   4-Br    4-Cl      5-Cl-thien-2-yl                                             4-Br    4-F       5-Cl-thien-2-yl                                             4-Br    4-OCF.sub.2 H                                                                           5-Cl-thien-2-yl                                             4-Br    4-CF.sub.3                                                                              5-Cl-thien-2-yl                                             4-Br    4-CN      5-Cl-thien-2-yl                                             4-Br    4-OCF.sub.3                                                                             5-Cl-thien-2-yl                                             4-Br    4-Cl      2-furyl                                                     4-Br    4-F       2-furyl                                                     4-Br    4-OCF.sub.2 H                                                                           2-furyl                                                     4-Br    4-CF.sub.3                                                                              2-furyl                                                     4-Br    4-CN      2-furyl                                                     4-Br    4-OCF.sub.3                                                                             2-furyl                                                     4-Br    4-Cl      3-furyl                                                     4-Br    4-F       3-furyl                                                     4-Br    4-OCF.sub.2 H                                                                           3-furyl                                                     4-Br    4-CF.sub.3                                                                              3-furyl                                                     4-Br    4-CN      3-furyl                                                     4-Br    4-OCF.sub.3                                                                             3-furyl                                                     ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        R.sub.1  K              R.sub.5   (m.p. °C.)                           ______________________________________                                        4-CF.sub.3                                                                             5-Cl-pyrid-2-yl                                                                              4-F       175 to 177                                  4-CF.sub.3                                                                             5-Cl-pyrid-2-yl                                                                              4-Cl                                                  4-CF.sub.3                                                                             5-Cl-pyrid-2-yl                                                                              4-CN                                                  4-CF.sub.3                                                                             5-Cl-pyrid-2-yl                                                                              4-CF.sub.3                                            4-CF.sub.3                                                                             5-Cl-pyrid-2-yl                                                                              3-Cl                                                  4-CF.sub.3                                                                             5-Cl-pyrid-2-yl                                                                              3,4-di-F                                              4-CF.sub.3                                                                             5-CF.sub.3 -pyrid-2-yl                                                                       4-F       180 to 182                                  4-CF.sub.3                                                                             5-CF.sub.3 -pyrid-2-yl                                                                       4-Cl                                                  4-CF.sub.3                                                                             5-CF.sub.3 -pyrid-2-yl                                                                       4-CN                                                  4-CF.sub.3                                                                             5-CF.sub.3 -pyrid-2-yl                                                                       4-CF.sub.3                                            4-CF.sub.3                                                                             5-CF.sub.3 -pyrid-2-yl                                                                       3-Cl                                                  4-CF.sub.3                                                                             5-CF.sub.3 -pyrid-2-yl                                                                       3,4-di-F                                              4-CF.sub.3                                                                             5-Br-pyrid-2-yl                                                                              4-F       199 to 200                                  4-CF.sub.3                                                                             5-Br-pyrid-2-yl                                                                              4-Cl                                                  4-CF.sub.3                                                                             5-Br-pyrid-2-yl                                                                              4-CN                                                  4-CF.sub.3                                                                             5-Br-pyrid-2-yl                                                                              4-CF.sub.3                                            4-CF.sub.3                                                                             5-Br-pyrid-2-yl                                                                              3-Cl                                                  4-CF.sub.3                                                                             5-Br-pyrid-2-yl                                                                              3,4-di-F                                              4-CF.sub.3                                                                             2-pyridyl      4-F                                                   4-CF.sub.3                                                                             2-pyridyl      4-Cl                                                  4-CF.sub.3                                                                             2-pyridyl      4-CN                                                  4-CF.sub.3                                                                             2-pyridyl      4-CF.sub.3                                            4-CF.sub.3                                                                             2-pyridyl      3-Cl                                                  4-CF.sub.3                                                                             2-pyridyl      3,4-di-F  168 to 170                                  4-CF.sub.3                                                                             3-pyridyl      4-F       197 to 200                                  4-CF.sub.3                                                                             3-pyridyl      4-Cl                                                  4-CF.sub.3                                                                             3-pyridyl      4-CN                                                  4-CF.sub.3                                                                             3-pyridyl      4-CF.sub.3                                            4-CF.sub.3                                                                             3-pyridyl      3-Cl                                                  4-CF.sub.3                                                                             3-pyridyl      3,4-di-F                                              4-CF.sub.3                                                                             2-Cl-pyrid-5-yl                                                                              4-F                                                   4-CF.sub.3                                                                             2-Cl-pyrid-5-yl                                                                              4-Cl                                                  4-CF.sub.3                                                                             2-Cl-pyrid-5-yl                                                                              4-CN                                                  4-CF.sub.3                                                                             2-Cl-pyrid-5-yl                                                                              4-CF.sub.3                                            4-CF.sub.3                                                                             2-Cl-pyrid-5-yl                                                                              3-Cl                                                  4-CF.sub.3                                                                             2-Cl-pyrid-5-yl                                                                              3,4-di-F                                              4-CF.sub.3                                                                             4-pyridyl      4-F                                                   4-CF.sub.3                                                                             4-pyridyl      4-Cl                                                  4-CF.sub.3                                                                             4-pyridyl      4-CN                                                  4-CF.sub.3                                                                             4-pyridyl      4-CF.sub.3                                            4-CF.sub.3                                                                             4-pyridyl      3-Cl                                                  4-CF.sub.3                                                                             4-pyridyl      3,4-di-F                                              4-CF.sub.3                                                                             2-pyrimidyl    4-F       220 to 221                                  4-CF.sub.3                                                                             2-pyrimidyl    4-Cl                                                  4-CF.sub.3                                                                             2-pyrimidyl    4-CN                                                  4-CF.sub.3                                                                             2-pyrimidyl    4-CF.sub.3                                            4-CF.sub.3                                                                             2-pyrimidyl    3-Cl                                                  4-CF.sub.3                                                                             2-pyrimidyl    3,4-di-F  196 to 199                                  4-CF.sub.3                                                                             4-pyrimidyl    4-F                                                   4-CF.sub.3                                                                             4-pyrimidyl    4-Cl                                                  4-CF.sub.3                                                                             4-pyrimidyl    4-CN                                                  4-CF.sub.3                                                                             4-pyrimidyl    4-CF.sub.3                                            4-CF.sub.3                                                                             4-pyrimidyl    3-Cl                                                  4-CF.sub.3                                                                             4-pyrimidyl    3,4-di-F                                              4-CF.sub.3                                                                             5-Cl-pyrimid-2-yl                                                                            4-F       195 to 200                                  4-CF.sub.3                                                                             5-Cl-pyrimid-2-yl                                                                            4-Cl                                                  4-CF.sub.3                                                                             5-Cl-pyrimid-2-yl                                                                            4-CN                                                  4-CF.sub.3                                                                             5-Cl-pyrimid-2-yl                                                                            4-CF.sub.3                                            4-CF.sub.3                                                                             5-Cl-pyrimid-2-yl                                                                            3-Cl                                                  4-CF.sub.3                                                                             5-Cl-pyrimid-2-yl                                                                            3,4-di-F  103 to 106                                  4-CF.sub.3                                                                             2-pyrazinyl    4-F                                                   4-CF.sub.3                                                                             2-pyrazinyl    4-Cl                                                  4-CF.sub.3                                                                             2-pyrazinyl    4-CN                                                  4-CF.sub.3                                                                             2-pyrazinyl    4-CF.sub.3                                            4-CF.sub.3                                                                             2-pyrazinyl    3-Cl                                                  4-CF.sub.3                                                                             2-pyrazinyl    3,4-di-F                                              4-CF.sub.3                                                                             3-pyridazinyl  4-F                                                   4-CF.sub.3                                                                             3-pyridazinyl  4-Cl                                                  4-CF.sub.3                                                                             3-pyridazinyl  4-CN                                                  4-CF.sub.3                                                                             3-pyridazinyl  4-CF.sub.3                                            4-CF.sub.3                                                                             3-pyridazinyl  3-Cl                                                  4-CF.sub.3                                                                             3-pyridazinyl  3,4-di-F                                              4-CF.sub.3                                                                             6-Cl-pyridazin-3-yl                                                                          4-F       200 to 202                                  4-CF.sub.3                                                                             6-Cl-pyridazin-3-yl                                                                          4-Cl                                                  4-CF.sub.3                                                                             6-Cl-pyridazin-3-yl                                                                          4-CN                                                  4-CF.sub.3                                                                             6-Cl-pyridazin-3-yl                                                                          4-CF.sub.3                                            4-CF.sub.3                                                                             6-Cl-pyridazin-3-yl                                                                          3-Cl                                                  4-CF.sub.3                                                                             6-Cl-pyridazin-3-yl                                                                          3,4-di-F                                              4-CF.sub.3                                                                             2-thiazolyl    4-F                                                   4-CF.sub.3                                                                             2-thiazolyl    4-Cl                                                  4-CF.sub.3                                                                             2-thiazolyl    4-CN                                                  4-CF.sub. 3                                                                            2-thiazolyl    4-CF.sub.3                                            4-CF.sub.3                                                                             2-thiazolyl    3-Cl                                                  4-CF.sub.3                                                                             2-thiazolyl    3,4-di-F                                              4-CF.sub.3                                                                             2-oxazolyl     4-F                                                   4-CF.sub.3                                                                             2-oxazolyl     4-Cl                                                  4-CF.sub.3                                                                             2-oxazolyl     4-CN                                                  4-CF.sub.3                                                                             2-oxazolyl     4-CF.sub.3                                            4-CF.sub.3                                                                             2-oxazolyl     3-Cl                                                  4-CF.sub.3                                                                             2-oxazolyl     3,4-di-F                                              4-CF.sub.3                                                                             1-Me-imidazol-2-yl                                                                           4-F                                                   4-CF.sub.3                                                                             1-Me-imidazol-2-yl                                                                           4-Cl                                                  4-CF.sub.3                                                                             1-Me-imidazol-2-yl                                                                           4-CN                                                  4-CF.sub.3                                                                             1-Me-imidazol-2-yl                                                                           4-CF.sub.3                                            4-CF.sub.3                                                                             1-Me-imidazol-2-yl                                                                           3-Cl                                                  4-CF.sub.3                                                                             1-Me-imidazol-2-yl                                                                           3,4-di-F                                              4-CF.sub.3                                                                             2-thienyl      4-F                                                   4-CF.sub.3                                                                             2-thienyl      4-Cl                                                  4-CF.sub.3                                                                             2-thienyl      4-CN                                                  4-CF.sub.3                                                                             2-thienyl      4-CF.sub.3                                            4-CF.sub.3                                                                             2-thienyl      3-Cl                                                  4-CF.sub.3                                                                             2-thienyl      3,4-di-F                                              4-CF.sub.3                                                                             2-furyl        4-F                                                   4-CF.sub.3                                                                             2-furyl        4-Cl                                                  4-CF.sub.3                                                                             2-furyl        4-CN                                                  4-CF.sub.3                                                                             2-furyl        4-CF.sub.3                                            4-CF.sub.3                                                                             2-furyl        3-Cl                                                  4-CF.sub.3                                                                             2-furyl        3,4-di-F                                              4-OCF.sub.3                                                                            5-Cl-pyrid-2-yl                                                                              4-F                                                   4-OCF.sub.3                                                                            5-Cl-pyrid-2-yl                                                                              4-Cl                                                  4-OCF.sub.3                                                                            5-Cl-pyrid-2-yl                                                                              4-CN                                                  4-OCF.sub.3                                                                            5-Cl-pyrid-2-yl                                                                              4-CF.sub.3                                            4-OCF.sub.3                                                                            5-Cl-pyrid-2-yl                                                                              3-Cl                                                  4-OCF.sub.3                                                                            5-Cl-pyrid-2-yl                                                                              3,4-di-F                                              4-OCF.sub.3                                                                            5-CF.sub.3 -pyrid-2-yl                                                                       4-F                                                   4-OCF.sub.3                                                                            5-CF.sub.3 -pyrid-2-yl                                                                       4-Cl                                                  4-OCF.sub.3                                                                            5-CF.sub.3 -pyrid-2-yl                                                                       4-CN                                                  4-OCF.sub.3                                                                            5-CF.sub.3 -pyrid-2-yl                                                                       4-CF.sub.3                                            4-OCF.sub.3                                                                            5-CF.sub.3 -pyrid-2-yl                                                                       3-Cl                                                  4-OCF.sub.3                                                                            5-CF.sub.3 -pyrid-2-yl                                                                       3,4-di-F                                              4-OCF.sub.3                                                                            2-pyridyl      4-F                                                   4-OCF.sub.3                                                                            2-pyridyl      4-Cl                                                  4-OCF.sub.3                                                                            2-pyridyl      4-CN                                                  4-OCF.sub.3                                                                            2-pyridyl      4-CF.sub.3                                            4-OCF.sub.3                                                                            2-pyridyl      3-Cl                                                  4-OCF.sub.3                                                                            2-pyridyl      3,4-di-F                                              4-OCF.sub. 3                                                                           3-pyridyl      4-F                                                   4-OCF.sub.3                                                                            3-pyridyl      4-Cl                                                  4-OCF.sub.3                                                                            3-pyridyl      4-CN                                                  4-OCF.sub.3                                                                            3-pyridyl      4-CF.sub.3                                            4-OCF.sub.3                                                                            3-pyridyl      3-Cl                                                  4-OCF.sub.3                                                                            3-pyridyl      3,4-di-F                                              4-OCF.sub.3                                                                            5-Cl-pyrimid-2-yl                                                                            4-F                                                   4-OCF.sub.3                                                                            5-Cl-pyrimid-2-yl                                                                            4-Cl                                                  4-OCF.sub.3                                                                            5-Cl-pyrimid-2-yl                                                                            4-CN                                                  4-OCF.sub.3                                                                            5-Cl-pyrimid-2-yl                                                                            4-CF.sub.3                                            4-OCF.sub.3                                                                            5-Cl-pyrimid-2-yl                                                                            3-Cl                                                  4-OCF.sub.3                                                                            5-Cl-pyrimid-2-yl                                                                            3,4-di-F                                              4-OCF.sub.3                                                                            4-pyrimidyl    4-F                                                   4-OCF.sub.3                                                                            4-pyrimidyl    4-Cl                                                  4-OCF.sub.3                                                                            4-pyrimidyl    4-CN                                                  4-OCF.sub.3                                                                            4-pyrimidyl    4-CF.sub.3                                            4-OCF.sub.3                                                                            4-pyrimidyl    3-Cl                                                  4-OCF.sub.3                                                                            4-pyrimidyl    3,4-di-F                                              4-OCF.sub.3                                                                            6-Cl-pyridazin-3-yl                                                                          4-F                                                   4-OCF.sub.3                                                                            6-Cl-pyridazin-3-yl                                                                          4-Cl                                                  4-OCF.sub.3                                                                            6-Cl-pyridazin-3-yl                                                                          4-CN                                                  4-OCF.sub.3                                                                            6-Cl-pyridazin-3-yl                                                                          4-CF.sub.3                                            4-OCF.sub.3                                                                            6-Cl-pyridazin-3-yl                                                                          3-Cl                                                  4-OCF.sub.3                                                                            6-Cl-pyridazin-3-yl                                                                          3,4-di-F                                              4-Cl     5-Cl-pyrid-2-yl                                                                              4-F                                                   4-Cl     5-Cl-pyrid-2-yl                                                                              4-Cl                                                  4-Cl     5-Cl-pyrid-2-yl                                                                              4-CN                                                  4-Cl     5-Cl-pyrid-2-yl                                                                              4-CF.sub.3                                            4-Cl     5-Cl-pyrid-2-yl                                                                              3-Cl                                                  4-Cl     5-Cl-pyrid-2-yl                                                                              3,4-di-F                                              4-Cl     5-CF.sub.3 -pyrid-2-yl                                                                       4-F                                                   4-Cl     5-CF.sub.3 -pyrid-2-yl                                                                       4-Cl                                                  4-Cl     5-CF.sub.3 -pyrid-2-yl                                                                       4-CN                                                  4-Cl     5-CF.sub.3 -pyrid-2-yl                                                                       4-CF.sub.3                                            4-Cl     5-CF.sub.3 -pyrid-2-yl                                                                       3-Cl                                                  4-Cl     5-CF.sub.3 -pyrid-2-yl                                                                       3,4-di-F                                              4-Cl     3-pyridyl      4-F       95                                          4-Cl     3-pyridyl      4-Cl                                                  4-Cl     3-pyridyl      4-CN                                                  4-Cl     3-pyridyl      4-CF.sub.3                                            4-Cl     3-pyridyl      3-Cl                                                  4-Cl     3-pyridyl      3,4-di-F                                              4-Cl     6-Cl-pyridazin-3-yl                                                                          4-F       207 to 210                                  4-Cl     6-Cl-pyridazin-3-yl                                                                          4-Cl                                                  4-Cl     6-Cl-pyridazin-3-yl                                                                          4-CN                                                  4-Cl     6-Cl-pyridazin-3-yl                                                                          4-CF.sub.3                                            4-Cl     6-Cl-pyridazin-3-yl                                                                          3-Cl                                                  4-Cl     6-Cl-pyridazin-3-yl                                                                          3,4-di-F                                              4-Cl     5-Cl-pyrimid-2-yl                                                                            4-F                                                   4-Cl     5-Cl-pyrimid-2-yl                                                                            4-Cl                                                  4-Cl     5-Cl-pyrimid-2-yl                                                                            4-CN                                                  4-Cl     5-Cl-pyrimid-2-yl                                                                            4-CF.sub.3                                            4-Cl     5-Cl-pyrimid-2-yl                                                                            3-Cl                                                  4-Cl     5-Cl-pyrimid-2-yl                                                                            3,4-di-F                                              4-Br     5-Cl-pyrid-2-yl                                                                              4-F                                                   4-Br     5-Cl-pyrid-2-yl                                                                              4-Cl                                                  4-Br     5-Cl-pyrid-2-yl                                                                              4-CN                                                  4-Br     5-Cl-pyrid-2-yl                                                                              4-CF.sub.3                                            4-Br     5-Cl-pyrid-2-yl                                                                              3-Cl                                                  4-Br     5-Cl-pyrid-2-yl                                                                              3,4-di-F                                              4-Br     5-CF.sub.3 -pyrid-2-yl                                                                       4-F                                                   4-Br     5-CF.sub.3 -pyrid-2-yl                                                                       4-Cl                                                  4-Br     5-CF.sub.3 -pyrid-2-yl                                                                       4-CN                                                  4-Br     5-CF.sub.3 -pyrid-2-yl                                                                       4-CF.sub.3                                            4-Br     5-CF.sub.3 -pyrid-2-yl                                                                       3-Cl                                                  4-Br     5-CF.sub.3 -pyrid-2-yl                                                                       3,4-di-F                                              4-Br     6-Cl-pyridazin-3-yl                                                                          4-F       244 to 245                                  4-Br     6-Cl-pyridazin-3-yl                                                                          4-Cl                                                  4-Br     6-Cl-pyridazin-3-yl                                                                          4-CN                                                  4-Br     6-Cl-pyridazin-3-yl                                                                          4-CF.sub.3                                            4-Br     6-Cl-pyridazin-3-yl                                                                          3-Cl                                                  4-Br     6-Cl-pyridazin-3-yl                                                                          3,4-di-F                                              4-CF.sub.3                                                                             5-Br-pyrimid-2-yl                                                                            4-F       196 to 198                                  ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                                                                 (m.p.                                R.sub.1                                                                              K             B       A      Y    °C.)                          ______________________________________                                        4-CF.sub.3                                                                           2-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           3-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           4-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           5-Cl-pyrid-2-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           5-CF.sub.3 -pyrid-2-yl                                                                      CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-Cl-pyrid-5-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           4-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           5-Cl-pyrimid-2-yl                                                                           CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-pyrazinyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           3-pyridazinyl CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           6-Cl-pyridazin-3-yl                                                                         CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-thiazolyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-oxazolyl    CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           1-Me-imidazol-2-yl                                                                          CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-thienyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-furyl       CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-CF.sub.3                                                                           2-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-CF.sub.3                                                                           4-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-CF.sub.3                                                                           2-Cl-pyrid-5-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-CF.sub.3                                                                           5-Cl-pyrid-2-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-CF.sub.3                                                                           5-CF.sub.3 -pyrid-2-yl                                                                      CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-CF.sub.3                                                                           4-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-CF.sub.3                                                                           6-Cl-pyridazin-3-yl                                                                         CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-Cl   2-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   3-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   4-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   5-Cl-pyrid-2-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   5-CF.sub.3 -pyrid-2-yl                                                                      CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-Cl-pyrid-5-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   4-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   5-Cl-pyrimid-2-yl                                                                           CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-pyrazinyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   3-pyridazinyl CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   6-Cl-pyridazin-3-yl                                                                         CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-thiazolyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-oxazolyl    CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   1-Me-imidazol-2-yl                                                                          CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-thienyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-furyl       CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-Cl   2-pyridyl     CH.sub.3                                                                              CO.sub. 2 Me                                                                         CH.sub.3                                  4-Cl   4-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-Cl   2-Cl-pyrid-3-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-Cl   5-Cl-pyrid-2-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-Cl   5-CF.sub.3 -pyrid-2-yl                                                                      CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-Cl   4-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-Cl   6-Cl-pyridazin-3-yl                                                                         CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-OCF.sub.3                                                                          2-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          3-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          4-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          5-Cl-pyrid-2-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          5-CF.sub.3 -pyrid-2-yl                                                                      CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-Cl-pyrid-5-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          4-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          5-Cl-pyrimid-2-yl                                                                           CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-pyrazinyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          3-pyridazinyl CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          6-Cl-pyridazin-3-yl                                                                         CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-thiazolyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-oxazolyl    CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          1-Me-imidazol-2-yl                                                                          CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-thienyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-furyl       CH.sub.3                                                                              CO.sub.2 Me                                                                          H                                         4-OCF.sub.3                                                                          2-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-OCF.sub.3                                                                          4-pyridyl     CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-OCF.sub.3                                                                          2-Cl-pyrid-3-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-OCF.sub.3                                                                          5-Cl-pyrid-2-yl                                                                             CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-OCF.sub.3                                                                          5-CF.sub.3 -pyrid-2-yl                                                                      CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-OCF.sub.3                                                                          4-pyrimidyl   CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  4-OCF.sub.3                                                                          6-Cl-pyridazin-3-yl                                                                         CH.sub.3                                                                              CO.sub.2 Me                                                                          CH.sub.3                                  ______________________________________                                    

                                      TABLE 4                                     __________________________________________________________________________    R.sub.1                                                                            R.sub.2                                                                          J       X Y         B  (m.p.°C.)                               __________________________________________________________________________    4-CF.sub.3                                                                         4-Cl                                                                             2-thienyl                                                                             S H         H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-thienyl                                                                             S H         H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       S H         H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       S H         H                                                 4-CF.sub.3                                                                         4-Cl                                                                             2-furyl S H         H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-furyl S H         H                                                 4-CF.sub.3                                                                         4-Cl                                                                             2-thienyl                                                                             O H         CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             3-thienyl                                                                             O H         CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O H         CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O H         CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             2-furyl O H         CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             3-furyl O H         CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             2-thienyl                                                                             O CH.sub.3  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-thienyl                                                                             O CH.sub.3  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O CH.sub.3  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O CH.sub.3  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             2-furyl O CH.sub.3  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-furyl O CH.sub.3  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             2-thienyl                                                                             O COCH.sub.3                                                                              H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-thienyl                                                                             O COCH.sub.3                                                                              H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O COCH.sub.3                                                                              H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O COCH.sub.3                                                                              H                                                 4-CF.sub.3                                                                         4-Cl                                                                             2-furyl O COCH.sub.3                                                                              H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-furyl O COCH.sub.3                                                                              H                                                 4-CF.sub.3                                                                         4-Cl                                                                             2-thienyl                                                                             O CO.sub.2 Me                                                                             H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-thienyl                                                                             O CO.sub.2 Me                                                                             H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O CO.sub.2 Me                                                                             H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O CO.sub.2 Me                                                                             H                                                 4-CF.sub.3                                                                         4-Cl                                                                             2-furyl O CO.sub.2 Me                                                                             H                                                 4-CF.sub.3                                                                         4-Cl                                                                             3-furyl O CO.sub.2 Me                                                                             H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       S H         CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       S CH.sub.3  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       S CH.sub.3  CH.sub.3                                          4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O H         Me 146 to 148                                     4-OCF.sub.3                                                                        4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O H         Me                                                4-I  4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O H         Me 192 to 195                                     4-Br 4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O H         Me 170 to 173                                     4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O H         Me 162 to 165                                     4-OCF.sub.3                                                                        4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O H         Me 161 to 163                                     4-Cl 4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O H         Me 158 to 161                                     4-Br 4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O H         Me 175 to 178                                     4-CF.sub.3                                                                         4-Cl                                                                             5-Br-thien-2-yl                                                                       O H         Me 182 to 185                                     4-OCF.sub.3                                                                        4-Cl                                                                             5-Br-thien-2-yl                                                                       O H         Me                                                4-Cl 4-Cl                                                                             5-Br-thien-2-yl                                                                       O H         Me                                                4-Br 4-Cl                                                                             5-Br-thien-2-yl                                                                       O H         Me 142 to 144                                     4-CF.sub.3                                                                         4-Cl                                                                             6-Cl-pyrid-2-yl                                                                       O H         Me 101.5 to 105                                   4-OCF.sub.3                                                                        4-Cl                                                                             6-Cl-pyrid-2-yl                                                                       O H         Me 108 to 110.5                                   4-Cl 4-Cl                                                                             6-Cl-pyrid-2-yl                                                                       O H         Me 132 to 134                                     4-Br 4-Cl                                                                             6-Cl-pyrid-2-yl                                                                       O H         Me                                                4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O H         Me foam (a)                                       4-OCF.sub.3                                                                        4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O H         Me gum (b)                                        4-Cl 4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O H         Me foam (c)                                       4-Br 4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O H         Me 91.5 to 95                                     4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O Me        Me 126 to 128                                     4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O Me        Me 115 to 119                                     4-CF.sub.3                                                                         4-Cl                                                                             6-Cl-pyrid-2-yl                                                                       O Me        Me 105 to 107.5                                   4-CF.sub.3                                                                         4-Cl                                                                             5-Br-thien-2-yl                                                                       O Me        Me 156 to 159                                     4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O Me        Me gum (d)                                        4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O S--N(Me)CO.sub.2 nBu                                                                    H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O S--N(Me)CO.sub.2 nBu                                                                    H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O S--N(Me)CO.sub.2 nBu                                                                    H                                                 4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O S--N(Me)CO.sub.2 nBu                                                                    H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O S--N(i-Pr)CO.sub.2 Et                                                                   H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O S--N(i-Pr)CO.sub.2 Et                                                                   H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O S--N(i-Pr)CO.sub.2 Et                                                                   H                                                 4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O S--N(i-Pr)CO.sub.2 Et                                                                   H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O S--N(Me)CO.sub.2 n-dec                                                                  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O S--N(Me)CO.sub.2 n-dec                                                                  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O S--N(Me)CO.sub.2 n-dec                                                                  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O S--N(Me)CO.sub.2 n-dec                                                                  H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O S--N(Me)SO.sub.2 Ph                                                                     H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O S--N(Me)SO.sub.2 Ph                                                                     H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O S--N(Me)SO.sub.2 Ph                                                                     H                                                 4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O S--N(Me)SO.sub.2 Ph                                                                     H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O S--CO.sub.2 -i-Bu                                                                       H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O S--CO.sub.2 -i-Bu                                                                       H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O S--CO.sub.2 -i-Bu                                                                       H                                                 4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O S--CO.sub.2 -i-Bu                                                                       H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-thien-2-yl                                                                       O S--P(O)(OEt).sub.2                                                                      H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Cl-pyrid-2-yl                                                                       O S--P(O)(OEt).sub.2                                                                      H                                                 4-CF.sub.3                                                                         4-Cl                                                                             5-Br-pyrid-2-yl                                                                       O S--P(O)(OEt).sub.2                                                                      H                                                 4-CF.sub.3                                                                         4-Cl                                                                             6-Br-pyrid-2-yl                                                                       O S--P(O)(OEt).sub.2                                                                      H                                                 __________________________________________________________________________     (a) υ max = 1670; (b) υ max = 1670; (c) υ max =       1670; (d) υ max = 1640                                                I.R. Carbonyl absorptions.                                               

                                      TABLE 5                                     __________________________________________________________________________    R.sub.1                                                                           K         R.sub.5                                                                          X Y         B  (m.p.°C.)                              __________________________________________________________________________    4-CF.sub.3                                                                        2-pyridyl 4-F                                                                              S H         H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              S H         H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              S H         H                                                4-CF.sub.3                                                                        3-pyridyl 4-F                                                                              S H         H                                                4-CF.sub.3                                                                        4-pyridyl 4-F                                                                              S H         H                                                4-CF.sub.3                                                                        6-Cl-pyridazin-3-yl                                                                     4-F                                                                              S H         H                                                4-CF.sub.3                                                                        4-pyrimidyl                                                                             4-F                                                                              S H         H                                                4-CF.sub.3                                                                        2-pyridyl 4-F                                                                              O H         CH.sub.3                                         4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O H         CH.sub.3                                         4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O H         CH.sub.3                                         4-CF.sub.3                                                                        3-pyridyl 4-F                                                                              O H         CH.sub.3                                         4-CF.sub.3                                                                        4-pyridyl 4-F                                                                              O H         CH.sub.3                                         4-CF.sub.3                                                                        6-Cl-pyridazin-3-yl                                                                     4-F                                                                              O H         CH.sub.3                                         4-CF.sub.3                                                                        4-pyrimidyl                                                                             4-F                                                                              O H         CH.sub.3                                         4-CF.sub.3                                                                        2-pyridyl 4-F                                                                              O CH.sub.3  H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O CH.sub.3  H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O CH.sub.3  H                                                4-CF.sub.3                                                                        3-pyridyl 4-F                                                                              O CH.sub.3  H                                                4-CF.sub.3                                                                        4-pyridyl 4-F                                                                              O CH.sub.3  H                                                4-CF.sub. 3                                                                       6-Cl-pyridazin-3-yl                                                                     4-F                                                                              O CH.sub.3  H                                                4-CF.sub.3                                                                        2-pyridyl 4-F                                                                              O COCH.sub.3                                                                              H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O COCH.sub.3                                                                              H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O COCH.sub.3                                                                              H                                                4-CF.sub.3                                                                        3-pyridyl 4-F                                                                              O COCH.sub.3                                                                              H                                                4-CF.sub.3                                                                        4-pyridyl 4-F                                                                              O COCH.sub.3                                                                              H                                                4-CF.sub.3                                                                        6-Cl-pyridazin-2-yl                                                                     4-F                                                                              O COCH.sub.3                                                                              H                                                4-CF.sub.3                                                                        4-pyrimidyl                                                                             4-F                                                                              O COCH.sub.3                                                                              H                                                4-CF.sub.3                                                                        2-pyridyl 4-F                                                                              O CO.sub.2 Me                                                                             H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O CO.sub.2 Me                                                                             H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O CO.sub.2 Me                                                                             H                                                4-CF.sub.3                                                                        3-pyridyl 4-F                                                                              O CO.sub.2 Me                                                                             H                                                4-CF.sub.3                                                                        4-pyridyl 4-F                                                                              O CO.sub.2 Me                                                                             H                                                4-CF.sub.3                                                                        6-Cl-pyridazin-3-yl                                                                     4-F                                                                              O CO.sub.2 Me                                                                             H                                                4-CF.sub.3                                                                        4-pyrimidinyl                                                                           4-F                                                                              O CO.sub.2 Me                                                                             H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              S CO.sub.2 Me                                                                             CH.sub.3                                         4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              S CH.sub.3  H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              S CH.sub.3  CH.sub.3                                         4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O S--N(Me)CO.sub.2 nBu                                                                    H                                                4-CF.sub.3                                                                        5-Br-pyrid-2-yl                                                                         4-F                                                                              O S--N(Me)CO.sub.2 nBu                                                                    H                                                4-CF.sub.3                                                                        5-CF.sub. 3 -pyrid-2-yl                                                                 4-F                                                                              O S--N(Me)CO.sub.2 nBu                                                                    H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O S--N(i-Pr)CO.sub.2 Et                                                                   H                                                4-CF.sub.3                                                                        5-Br-pyrid-2-yl                                                                         4-F                                                                              O S--N(i-Pr)CO.sub.2 Et                                                                   H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O S--N(i-Pr)CO.sub.2 Et                                                                   H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O S--N(Me)SO.sub.2 Ph                                                                     H                                                4-CF.sub.3                                                                        5-Br-pyrid-2-yl                                                                         4-F                                                                              O S--N(Me)SO.sub.2 Ph                                                                     H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O S--N(Me)SO.sub.2 Ph                                                                     H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O S--CO.sub.2 i-Bu                                                                        H                                                4-CF.sub.3                                                                        5-Br-pyrid-2-yl                                                                         4-F                                                                              O S--CO.sub.2 i-Bu                                                                        H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O S--CO.sub.2 i-Bu                                                                        H                                                4-CF.sub.3                                                                        5-Cl-pyrid-2-yl                                                                         4-F                                                                              O S--P(O)(OEt).sub.2                                                                      H                                                4-CF.sub.3                                                                        5-Br-pyrid-2-yl                                                                         4-F                                                                              O S--P(O)(OEt).sub.2                                                                      H                                                4-CF.sub.3                                                                        5-CF.sub.3 -pyrid-2-yl                                                                  4-F                                                                              O S--P(O)(OEt).sub.2                                                                      H                                                __________________________________________________________________________

Formulation and Use

The compounds of this invention will generally be used in formulationwith a carrier comprising a liquid or solid diluent or an organicsolvent. Useful formulations of the compounds of Formula I can beprepared in conventional ways. They include dusts, granules, pellets,solutions, suspensions, emulsions, wettable powders, emulsifiableconcentrates, dry flowables and the like. Many of these can be applieddirectly. Sprayable formulations can be extended in suitable media andused at spray volumes of from about one to several hundred liters perhectare. High strength compositions are primarily used as intermediatesfor further formulation. The formulations, broadly, contain about 1% to99% by weight of active ingredient(s) and at least one of a) about 0.1%to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s).More specifically, they will contain these ingredients in the followingapproximate proportions:

    ______________________________________                                                    Percent by Weight                                                             Active                                                                        Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            25-90      0-74     1-10                                        Oil Suspensions,                                                                             1-50     40-95     0-35                                        Emulsions, Solutions                                                          (including Emulsifiable                                                       Concentrates)                                                                 Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                         1-95      5-99     0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                    

Lower or high levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J. The more absorptive diluents are preferred for wettablepowders and the denser ones for dusts. Typical liquid diluents andsolvents are described in Marsden, "Solvents Guide," 2nd Ed.,Interscience, New York, 1950. Solubility under 0.1% is preferred forsuspension concentrates; solution concentrates are preferably stableagainst phase separation at 0° C. "McCutcheon's Detergents andEmulsifiers Annual", Allured Publ. Corp., Ridgewood, N.J., as well asSisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ.Co., Inc., New York, 1964, list surfactants and recommended uses. Allformulations can contain minor amounts of additives to reduce foam,caking, corrosion, microbiological growth, etc. Preferably, ingredientsshould be approved by the U.S. environmental Protection Agency for theuse intended.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example, U.S.Pat. No. 3,060,084). Granules and pellets can be made by spraying theactive material upon preformed granular carriers or by agglomerationtechniques. See Browning, "Agglomeration", Chemical Engineering, Dec. 4,1967, pages 147 and following, and "Perry's Chemical Engineer'sHandbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 andfollowing.

Many of the compounds of the invention are most efficacious when appliedin the form of an emulsifiable concentrate mixed with a spray oil orspray oil concentrate. Although any oil can be used as a spray oil,spray oils usually have these characteristics: they are not phytotoxicto the crop sprayed, and they have appropriate viscosity. Petroleumbased oils are commonly used for spraying. In some areas, crop oils arepreferred such as the following:

    ______________________________________                                        Common Crop Oils Used as Spray Oils                                           ______________________________________                                        Corn Oil            Linseed Oil                                               Cottonseed Oil      Soybean Oil                                               Coconut Oil         Sunflower Oil                                             Rapeseed Oil        Olive Oil                                                 Peanut Oil          Palm Oil                                                  Safflower Oil       Sesame Oil                                                Mustardseed Oil     Caster Oil                                                ______________________________________                                    

The following oils also meet the criteria for a spray oil: mineral, fishand cod liver oil.

Spray oil concentrates comprise a spray oil together with one or moreadditional ingredients such as emulsifiers and wetting agents. A numberof useful spray oil and spray oil concentrates can be found in "A Guideto Agricultural Spray Adjuvants Used in the United States" by Thomson,Thomson Publications, California, 1986.

Examples of useful formulations of compounds of the present inventionare as follows:

EXAMPLE 7 Emulsifiable Concentrate

    ______________________________________                                        5-(5-chloro-2-thienyl)-1-(4-fluorophenyl)-4,5-dihydro-                                                   20%                                                N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-car-                              boxamide                                                                      blend of oil soluble sulfonates                                                                          10%                                                and polyoxyethylene ethers                                                    isophorone                 70%                                                ______________________________________                                    

The ingredients are combined and stirred with gentle warming to speedsolution. A fine screen filter is included in packaging operation toinsure the absence of any extraneous undissolved material in theproduct.

EXAMPLE 8 Wettable Powder

    ______________________________________                                        1-(4-chlorophenyl)-5-(5-chloro-2-thienyl)-4,5-dihydro-                                                    30%                                               N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxa-                          mide                                                                          sodium alkylnaphthalenesulfonate                                                                           2%                                               sodium ligninsulfonate       2%                                               synthetic amorphous silica   3%                                               kaolinite                   63%                                               ______________________________________                                    

The active ingredient is mixed with the inert materials in a blender.After grinding in a hammer-mill, the material is re-blended and siftedthrough a 50 mesh screen.

EXAMPLE 9 Dust

    ______________________________________                                        Wettable powder of Example 8                                                                        10%                                                     pyrophyllite (powder) 90%                                                     ______________________________________                                    

The wettable powder and the pyrophyllite diluent are thoroughly blendedand then packaged. The product is suitable for use as a dust.

EXAMPLE 10 Granule

    ______________________________________                                        1-(5-chloro-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro-                                                  10%                                               N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxa-                          mide                                                                          attapulgite granules (low volative                                                                        90%                                               matter, 0.71/0.30 mm; U.S.S. No.                                              25-50 sieves)                                                                 ______________________________________                                    

The active ingredient is dissolved in a volatile solvent such as acetoneand sprayed upon dedusted and pre-warmed attapulgite granules in adouble cone blender. The acetone is then driven off by heating. Thegranules are then allowed to cool and are packaged.

EXAMPLE 11 Granule

    ______________________________________                                        Wettable powder of Example 8                                                                        15%                                                     gypsum                69%                                                     potassium sulfate     16%                                                     ______________________________________                                    

The ingredients are blended in a rotating mixer and water sprayed on toaccomplish granulation. When most of the material has reached thedesired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), thegranules are removed, dried, and screened. Oversize material is crushedto produce additional material in the desired range. These granulescontain 4.5% active ingredient.

EXAMPLE 12 Solution

    ______________________________________                                        1-(6-chloro-3-pyridazinyl)-5-(4-fluorophenyl)-4,5-                                                       25%                                                dihydro-N-]4-(trifluoromethyl)phenyl]-1H-pyrazole-                            3-carboxamide                                                                 N-methyl-pyrrolidone       75%                                                ______________________________________                                    

The ingredients are combined and stirred to produce a solution suitablefor direct, low volume application.

EXAMPLE 13 Aqueous Suspension

    ______________________________________                                        5-(5-chloro-2-thienyl)-1-(4-fluorophenyl)-4,5-dihydro-                                                     40%                                              N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxa-                          mide                                                                          polyacrylic acid thickener    0.3%                                            dodecyclophenol polyethylene glycol                                                                         0.5%                                            ether                                                                         disodium phosphate            1.0%                                            monosodium phosphate          0.5%                                            polyvinyl alcohol             1.0%                                            water                        56.7%                                            ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 14 Oil Suspension

    ______________________________________                                        1-(4-chlorophenyl)-5-(5-chloro-2-thienyl)-4,5-                                                           35.0%                                              dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-                            3-carboxamide                                                                 blend of polyalcohol carboxylic                                                                           6.0%                                              esters and oil soluble petroleum                                              sulfonates                                                                    xylene range solvent       59.0%                                              ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 15 Bait Granules

    ______________________________________                                        1-(5-chloro-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro-                                                   3.0%                                             N-[4-(triflyoromethyl)phenyl]-1H-pyrazole-3-carboxa-                          mide                                                                          blend of polyethoxylated nonyl-                                                                            9.0%                                             phenols and sodium dodecyl-                                                   benzene sulfonates                                                            ground up corn cobs          88.0%                                            ______________________________________                                    

The active ingredient and surfactant blend are dissolved in a suitablesolvent such as acetone and sprayed onto the ground corn cobs. Thegranules are then dried and packaged. Compounds of Formula I can also bemixed with one or more other insecticides, fungicides, nematocides,bactericides, acaricides, or other biologically active compounds to forma multi-component pesticide giving an even broader spectrum of effectiveagricultural protection. Examples of other agricultural protectants withwhich compounds of the present invention can be mixed or formulated are:

Insecticides

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol(carbofuran)

O-[2,4,5-trichloro-α-(chloromethyl)benzyl]phosphoric acid,O',O'-dimethyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoricacid, dimethyl ester (malathion)

phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methylparathion)

methylcarbamic acid, ester with α-naphthol (carbaryl)

methyl O-(methylcarbamoyl)thiolacetohydroxamate (methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine (chlorodimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphosphorothioate(diazinon)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN)

(S)-α-cyano-m-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate(deltamethrin)

Methyl N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-1-thiooxamimidate(oxamyl)

cyano(3-phenoxyphenyl)-methyl-4-chloro-α-(1-methylethyl)benzeneacetate(fenvalerate)

(3-phenoxyphenyl)methyl(±)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate(permethrin)

α-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (cypermethrin)

O-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate (profenofos)

phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propylester (sulprofos).

Additional insecticides are listed hereafter by their common names:triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb,acephate, azinphos-methyl, chlorpyrifos, dimethoate, fonophos,isofenphos, methidathion, methamidiphos, monocrotophos, phosmet,phosphamidon, phosalone, pirimicarb, phorate, profenofos, terbufos,trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin,fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde androtenone.

Fungicides

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl)

1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole(propiconazole)

2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil)

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone(triadimefon)

N-(trichloromethylthio)tetrahydrophthalimide (captan)

N-(trichloromethylthio)phthalimide (folpet)

1-[[[bis(4-fluorophenyl)][methyl]silyl]methyl]-1H-1,2,4-triazole.

Nematocides

S-methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate

S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethylO'-[4-(methylthio)-m-tolyl]diester (fenamiphos).

Bactericides

tribasic copper sulfate

streptomycin sulfate.

Acaricides

senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl)

6-methyl-1,3-dithiolo[4,5-β]quinoxalin-2-one (oxythioquinox)

ethyl 4,4'-dichlorobenzilate (chlorobenzilate)

1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol (dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor)

tricyclohexyltin hydroxide (cyhexatin)

trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3-carboxamide(hexythiazox)

amitraz

propargite

fenbutatin-oxide

bisclofentezin.

Biological

Bacillus thuringiensis

Avermectin B.

Utility

The compounds of the present invention exhibit activity against a widespectrum of foliar and soil inhabiting insects. Those skilled in the artwill recognize that not all compounds are equally effective against allinsects, but the compounds of this invention display activity againsteconomically important pest species, such as grasshoppers andcockroaches; thrips; hemipterans; plant bugs (Miridae), such astarnished plant bug, lace bugs (Tingidae), seed bugs (Lygaeidae) such ascinch bugs, stink bugs (Pentatomidae), leaf-footed bugs (Coreidae), suchas squash bug, and red bugs and stainers (Pyrrhocoridae) such as cottonstainer; also homopterans such as whiteflies, aphids such as the greenpeach aphid, greenbug and cotton aphid, leafhoppers, spittlebugs andplant hoppers such as aster leafhopper, potato leafhopper and riceplanthoppers, psyllids such as pear psylla, scales (coccids anddiaspidids) and mealybugs; coleopterans including weevils, such as bollweevil and rice water weevil, grain borers, chrysomellid beetles, suchas Colorado potato beetle, flea beetles and other leaf beetles,coccinellid beetles such as Mexican bean beetle, and soil insects suchas southern corn rootworm and wireworm; lepidopterous larvae includingnoctuids such as fall armyworm, beet armyworm, other Spodoptera spp.,Heliothis virescens, Heliothis zea, cabbage looper, green cloverworm,velvetbean caterpillar, cotton leafworm, black cutworm, and othernoctuid cutworms and including pyralids such as European corn borer,navel orangeworm, and stalk/stem borers and including tortricids likecodling moth and grape berry moth as well as other lepidopterous larvae,such as pink bollworm and diamondback moth; and dipterans such asleafminers, soil maggots, midges, tephritid fruit flies. The specificspecies, for which control is exemplified below, are: fall armyworm,Spodoptera frugiperda; tobacco budworm, Heliothis virescens; bollweevil, Anthonomus grandis; European corn borer, Ostrinia nubilalis;southern corn rootworm, Diabrotica undecimpunctata howardi; asterleafhopper, Macrosteles fascifrons. The pest control afforded by thecompounds of the present invention is not limited, however, to thesespecies.

Application

Insects are controlled and agricultural crops are protected by applyingone or more of the Formula I compounds of this invention, in aneffective amount, to the locus of infestation, to the area to beprotected, or directly on the pests to be controlled. A preferred methodof application is by spraying with spray equipment that distributes thecompound on the foliage, in the soil, or to the plant part that isinfested or needs to be protected. Alternatively granular formulationsof these compounds can be applied to soil or foliage or, optionally,incorporated into the soil. Either aerial or ground application can beused.

The pyrazoline compound(s) of this invention can be applied directly,but most often application will be of a formulation comprising one ormore compounds of this invention, in an agriculturally suitable carrieror diluent. A most preferred method of application involves spraying awater dispersion or refined oil solution of the compounds. Combinationswith spray oils and spray oil concentrations often enhance the efficacyof the compounds of Formula I.

The rate of application of the Formula I compounds required foreffective control will depend on such factors as the species of insectto be controlled, the pest's life stage, its size, its loction, the hostcrop, time of year of application, ambient moisture, temperatureconditions, and the like. In general, application rates of 0.05 to 2 kgof active ingredient per hectare are sufficient to provide effectivecontrol in large scale field operations under normal circumstances, butas little as 0.001 kg/hectare may be sufficient or as much as 8kg/hectare may be required, depending upon the factors listed above. Theaddition of a compound such as piperonyl butoxide, can enhance theinsecticidal activity of many of the compounds of Formula I.

The following examples demonstrate the control efficacy of compounds ofFormula I on specific insect pests wherein Compounds 1 through 31 aredescribed in Table 6.

                  TABLE 6                                                         ______________________________________                                         ##STR20##                Compound 1                                           ##STR21##                Compound 2                                           ##STR22##                Compound 3                                           ##STR23##                Compound 4                                           ##STR24##                Compound 5                                           ##STR25##                Compound 6                                           ##STR26##                Compound 7                                           ##STR27##                Compound 8                                           ##STR28##                Compound 9                                           ##STR29##                Compound 10                                          ##STR30##                Compound 11                                          ##STR31##                Compound 12                                          ##STR32##                Compound 13                                          ##STR33##                Compound 14                                          ##STR34##                Compound 15                                          ##STR35##                Compound 16                                          ##STR36##                Compound 17                                          ##STR37##                Compound 18                                          ##STR38##                Compound 19                                          ##STR39##                Compound 20                                          ##STR40##                Compound 21                                          ##STR41##                Compound 22                                          ##STR42##                Compound 23                                          ##STR43##                Compound 24                                          ##STR44##                Compound 25                                          ##STR45##                Compound 26                                          ##STR46##                Compound 27                                          ##STR47##                Compound 28                                          ##STR48##                Compound 29                                          ##STR49##                Compound 30                                          ##STR50##                Compound 31                                         ______________________________________                                    

EXAMPLE 16 Fall Armyworm

Test units, each consisting of an 8-ounce plastic cup containing a layerof wheat germ diet, approximately 0.5 cm thick, were prepared. Tenthird-instar larvae of fall armyworm (Spodoptera frugiperda) were placedinto each cup. Solutions of each of the test compounds(acetone/distilled water 75/25 solvent) were sprayed onto the cups, asingle solution per set of three cups. Spraying was accomplished bypassing the cups, on a conveyer belt, directly beneath a flat fanhydraulic nozzle which discharged the spray at a rate of 0.5 pounds ofactive ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. The cups werethen covered and held at 27° C. and 50% relative humidity for 72 hours,after which time readings were taken. Of the compounds tested on fallarmyworm, the following resulted in greater than or equal to 80%mortality: 1, 3, 4, 5, 6, 7, 8, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20,21, 22, 23, 24, 25, 26, 27, 28, 29, 30 and 31.

EXAMPLE 17 Tobacco Budworm

The test procedure of Example 16 was repeated for efficacy againstthird-instar larvae of the tobacco budworm (Heliothis virescens) exceptthat mortality was assessed at 48 hours. Of the compounds tested ontobacco budworm, the following resulted in greater than or equal to 80%mortality: 7, 8, 10, 11, 12, 13, 14, 17, 19, 20, 21, 22, 23, 24, 25, 26,27, 28 and 29.

EXAMPLE 18 European Corn Borer

Test units, each consisting of an 8-ounce plastic cup containingone-inch square of wheat germ/soyflour diet, were prepared. Fivethird-instar larvae of the European corn borer (Ostrinia nubilalis) wereplaced into each cup. Sets of three test units were sprayed as describedin Example 16 with individual solutions of the test compounds. The cupswere then covered and held at 27° C. and 50% relative humidity for 48hours, after which time mortality readings were taken. Of the compoundstested on European corn borer, the following resulted in greater than orequal to 80% mortality: 1, 3, 4, 6, 7, 8, 9 and 10.

EXAMPLE 19 Southern Corn Rootworm

Test units, each consisting of an 8-ounce plastic cup containing 1sprouted corn seed (Zea mays), were prepared. Sets of three test unitswere sprayed as described in Example 16 with individual solutions of thetest compounds. After the spray on the cups had dried, five third-instarlarvae of the southern corn rootworm (Diabrotica undecimpunctatahowardi) were placed into each cup. A moistened dental wick was insertedinto each cup to prevent drying and the cups were then covered. The cupswere then held at 27° C. and 50% relative humidity for 48 hours, afterwhich time mortality readings were taken. Of the compounds tested onsouthern corn rootworm, the following resulted in greater than or equalto 80% mortality: 4, 7, 11, 13, 15, 19, 21, 22, 23, 24, 25, 26, 27, 28,29 and 31.

EXAMPLE 20 Boll Weevil

Five adult boll weevils (Anthonomus grandis) were placed into each of aseries of 9-ounce cups. The test procedure employed was then otherwisethe same as in Example 16 with three cups per treatment. Mortalityreadings were taken 48 hours after treatment. Of the compounds tested onboll weevil, the following resulted in greater than or equal to 80%mortality: 1, 2, 7, 9, 10, 27, 28, 29 and 30.

EXAMPLE 21 Aster Leafhopper

Test units were prepared from a series of 12-ounce cups, each containingoat (Avena sativa) seedlings in a 1-inch layer of sterilized soil. Setsof three test units were sprayed as described in Example 16 withindividual solutions of the test compounds. After the oats had driedfrom the spraying, between 10 and 15 adult aster leafhoppers(Mascrosteles fascifrons) were aspirated into each of the covered cups.The cups were held at 27° C. and 50% relative humidity for 48 hours,after which time mortality readings were taken. Of the compounds testedon aster leafhopper, the following resulted in greater than or equal to80% mortality: 7, 8, 19, 20, 21, 23, 24 and 27.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. A compound of theformula ##STR51## wherein: X is O or S;Y is selected from the group H,C₁ to C₄ alkyl, C₂ to C₄ alkoxyalkyl, C₁ to C₄ alkylthio, C₁ to C₄haloalkylthio, SX', phenylthio, or phenylthio substituted with 1 to 3substituents independently selected from W, C₂ to C₄ alkoxycarbonyl,C(O)H, C₂ to C₄ alkylcarbonyl and C₂ to C₄ haloalkylcarbonyl; A isselected from the group H, C₁ to C₆ alkyl, phenyl, phenyl substituted by(R₅)_(p), CN, CO₂ R₃, C(O)R₃, C(O)NR₃ R₄, C(S)NR₃ R₄, C(S)R₃, C(S)SR₃ ;B is selected from the group H, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₂to C₆ alkoxyalkyl, C₂ to C₆ cyanoalkyl, C₃ to C₈ alkoxycarbonylalkyl, C₂to C₆ alkenyl, C₂ to C₆ alkynyl, C₂ to C₆ alkoxycarbonyl, phenyl, phenylsubstituted with 1 to 3 substituents independently selected from W,benzyl and benzyl substituted with 1 to 3 substituents independentlyselected from W; W is selected from the group halogen, CN, NO₂, C₁ to C₂alkyl, C₁ to C₂ haloalkyl, C₁ to C₂ alkoxy, C₁ to C₂ haloalkoxy, C₁ toC₂ alkylthio, C₁ to C₂ haloalkylthio, C₁ to C₂ alkylsulfonyl and C₁ toC₂ haloalkylsulfonyl; R is ##STR52## R₁, R₂ and R₅ are independentlyselected from the group R₃, halogen, CN, N₃, SCN, NO₂, OR₃, SR₃, S(O)R₃,S(O)₂ R₃, OC(O)R₃, OS(O)₂ R₃, CO₂ R₃, C(O)R₃, C(O)NR₃ R₄, S(O)₂ NR₃ R₄,NR₃ R₄, NR₄ C(O)R₃, OC(O)NHR₃, NR₄ C(O)NHR₃, NR₄ S(O)₂ R₃ ; R₃ isselected from the group H, C₁ to C₄ alkyl, C₁ to C₄ haloalkyl, C₂ to C₄alkenyl, C₂ to C₄ haloalkenyl, C₂ to C₄ alkynyl, C₂ to C₄ haloalkynyl,C₂ to C₄ alkoxyalkyl, C₂ to C₄ alkylthioalkyl, C₁ to C₄ nitroalkyl, C₁to C₄ cyanoalkyl, C₃ to C₆ alkoxycarbonylalkyl, C₃ to C₆ cycloalkyl, C₃to C₆ halocycloalkyl, phenyl, benzyl, or phenyl or benzyl substitutedwith 1 to 3 substituents independently selected from W; R₄ is H or C₁ toC₄ alkyl; X' is ##STR53## R₆ and R₁₀ are independently selected from C₁to C₆ alkyl, C₁ -C₆ haloalkyl, C₃ -C₆ cycloalkyl, C₄ -C₇cycloalkylalkyl, C₂ to C₆ cyanoalkyl, C₂ to C₆ alkoxyalkyl, C₃ to C₈alkoxycarbonylalkyl, C₄ to C₈ dialkylaminocarbonylalkyl, phenyloptionally substituted by 1 to 2 substituents selected from W, benzyloptionally substituted by 1 to 2 substituents selected from W, andphenethyl optionally substituted by 1 to 2 substituents selected from W;R is F, C₁ -C₂₀ alkyl, C₁ -C₆ haloalkyl, C₂ -C₈ dialkylamino, phenyloptionally substituted by 1 to 2 substituents selected from W, or R₇ isC₁ -C₂₀ alkoxy, C₁ -C₄ alkoxy substituted by cyano, nitro, C₁ -C₄alkoxy, C₄ -C₈ alkoxyalkoxy, C₁ -C₂ alkylthio, C₂ -C₃ alkoxycarbonyl, C₃-C₅ dialkylaminocarbonyl, phenyl or 1 to 6 halogens, or R₇ is phenoxyoptionally substituted by 1 to 2 substituents selected from W, R₈ and R₉are independently selected from C₁ -C₄ alkyl, C₂ -C₄ haloalkyl or phenyloptionally substituted by 1 to 2 substituents selected from W;a is 0 to2; Y' is O or S; m is 1 to 3; n is 0 to 3; and p is 0 to
 3. 2. Acompound according to claim 1 wherein:X is O; Y is H, CH₃, SCH₃, SCCl₃,SC₆ H₅, 2-(NO₂)C₆ H₄ S, C(O)CH₃, C(O)H, C(O)CF₃, CO₂ CH₃, CO₂ C₂ H₅ orSX'; X' is X₁, X₂, X₃, X₄, X₅ or X₇ ; R₆ and R₁₀ are independentlyselected from C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₅ -C₆ cycloalkyl, C₃ -C₈alkoxycarbonylalkyl, phenyl, benzyl or phenethyl each optionallysubstituted with W; R₈ and R₉ are independently selected from C₁ -C₃alkyl and phenyl; a is 2; R₃ is C₁ to C₄ alkyl, C₁ to C₂ haloalkyl, C₂to C₄ alkenyl, C₂ to C₄ haloalkenyl, propargyl, phenyl, benzyl; orphenyl or benzyl substituted with one of F, Cl, Br, CF₃, OCF₂ H, OCF₃ orNO₂ ; B is H, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₂ to C₆ alkoxyalkyl,C₂ to C₆ cyanoalkyl, C₃ to C₈ alkoxycarbonylalkyl, C₁ to C₆ alkenyl, C₁to C₆ alkynyl or C₂ to C₆ alkoxycarbonyl; n is 0 to 2; and m is 1 to 2.3. A compound according to claim 2 wherein:R₁ is halogen, CN, SCN, NO₂,R₃, OR₃, SR₃, S(O)₂ R₃, CO₂ R₃ or C(O)R₃ ; R₂ is halogen, CN, SCN, NO₂,R₃, OR₃, SR₃, S(O)₂ R₃, OC(O)R₃, OS(O)₂ R₃, CO₂ R₃, C(O)R₃, C(O)NR₃ R₄,S(O)₂ NR₃ R₄ or NR₃ R₄ ; R₃ is C₁ to C₄ alkyl, C₁ to C₂ haloalkyl, C₂ toC₄ alkenyl, C₂ to C₄ haloalkenyl or propargyl; R₄ is H or C₁ to C₂alkyl; W is halogen, CN, CO₂ CH₃, C(O)NHCH₃, C(O)N(CH₃)₂, NO₂, CH₃, CF₃,OCH₃, OCF₂ H, OCF₂ CF₂ H, SCH₃, SCF₂ H, SCF₂ CF₂ H or S(O)₂ CH₃ ; B isH, C₁ to C₄ alkyl, C₁ to C₄ haloalkyl, or C₃ to C₄ alkenyl.
 4. Acompound according to claim 3 wherein:Y is H, CH₃, C(O)CH₃, CO₂ CH₃ orSX'; X' is X₁, X₂, X₃ or X₅ ; R₆ is C₁ -C₄ alkyl, CF₃, cyclohexyl,phenyl optionally substituted by W, or benzyl optionally substituted byW; R₇ is F, C₁ -C₁₂ alkyl, C₁ -C₆ haloalkyl, phenyl or phenoxy eachoptionally substituted by W, C₁ -C₁₂ alkoxy, dimethylamino or C₁ -C₄alkoxy substituted with NO₂, C₂ -C₄ alkoxy or 1-6 halogens; m is 1 or 2and one substituent is in the 4-position of the phenyl ring; n is 0, 1or 2 and one substituent is in the 4-position of the phenyl ring; R₁ isF, Cl, Br, CF₃, OCF₂ H, OCF₃, CN; R₂ is F, Cl, Br, CN, NO₂, CF₃, CH₃,OCH₃, OCF₂ H, OCF₃, SCH₃, SCF₂ H, S(O)₂ CH₃ or N(CH₃)₂ ; and B is H orCH₃.
 5. A compound according to claim 1 wherein:A is H, C₁ to C₆ alkyl,phenyl, phenyl substituted by (R₅)_(p), CO₂ R₃, C(O)R₃, C(O)NR₃ R₄,C(S)NR₃ R₄, C(S)R₃ or C(S)SR₃.
 6. A compound according to claim 5wherein:X is O; Y is H, CH₃, SCH₃, SCCl₃, SC₆ H₅, 2-(NO₂)C₆ H₄ S,C(O)CH₃, C(O)H, C(O)CF₃, CO₂ CH₃ or CO₂ C₂ H₅ ; R₃ is C₁ to C₄ alkyl, C₁to C₂ haloalkyl, C₂ to C₄ alkenyl, C₂ to C₄ haloalkenyl, propargyl,phenyl, benzyl, or phenyl or benzyl substituted with one of F, Cl, Br,CF₃, OCF₂ H, OCF₃ or NO₂ ; m is 1 to 2; and p is 0 to
 2. 7. A compoundaccording to claim 6 wherein:R₁ is halogen, CN, SCN, NO₂, R₃, OR₃, SR₃,S(O)₂ R₃, CO₂ R₃ or C(O)R₃ ; R₃ is C₁ to C₄ alkyl, C₁ to C₂ haloalkyl,C₂ to C₄ alkenyl, C₂ to C₄ haloalkenyl or propargyl; R₄ is H or C₁ to C₂alkyl; R₅ is halogen, CN, SCN, NO₂, R₃, OR₃, SR₃, S(O)₂ R₃, OC(O)R₃,OS(O)₂ R₃, CO₂ R₃, C(O)R₃, C(O)NR₃ R₄, S(O)₂ NR₃ R₄ or NR₃ R₄ ; W ishalogen, CN, CO₂ CH₃, C(O)NHCH₃, C(O)N(CH₃)₂, NO₂, CH₃, CF₃, OCH₃, OCF₂H, OCF₂ CF₂ H, SCH₃, SCF₂ H, SCF₂ CF₂ H or S(O)₂ CH₃ ; A is C₁ to C₄alkyl, phenyl, phenyl substituted with (R₅)_(p), CO₂ R₃, C(O)R₃, C(O)NR₃R₄ or C(O)NR₄ phenyl said phenyl optionally substituted with F, Cl, Br,CF₃, OCF₂ H, OCF₃ or NO₂ ; B is H, C₁ to C₄ alkyl, C₁ to C₄ haloalkyl,or C₃ to C₄ alkenyl; and R₆ is H or C₁ to C₂ alkyl.
 8. A compoundaccording to claim 7 wherein:Y is H, CH₃, C(O)CH₃ or CO₂ CH₃ ; R₁ is F,Cl, Br, CF₃, OCF₂ H, OCF₃, CN; R₅ is F, Cl, Br, CN, NO₂, CF₃, CH₃, OCH₃,OCF₂ H, OCF₃, SCH₃, SCF₂ H, S(O)₂ CH₃, S(O)₂ CF₂ H, CO₂ CH₃, C(O)NHCH₃,C(O)N(CH₃)₂, S(O)₂ N(CH₃)₂ or N(CH₃)₂ ; A is phenyl substituted with(R₅)_(p) ; B is H or CH₃ ; m is 1 or 2 and one substituent is in the4-position of the phenyl ring; and p is 1 or 2 and one substituent is inthe 3 or 4-position of the phenyl ring.
 9. A compound according to claim7 wherein:Y is H, CH₃, C(O)CH₃ or CO₂ CH₃ ; R₁ is F, Cl, Br, CF₃, OCF₂H, OCF₃, CN; A is CO₂ CH₃, CO₂ C₂ H₅, C(O)NHCH₃ or C(O)N(CH₃)₂ ; B isCH₃ ; and m is 1 or 2 and one substituent is in the 4-position of thephenyl ring.
 10. A compound according to claim 8:1-(5-chloro-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide.11. A compound according to claim 8:1-(5-bromo-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide.12. A composition comprising an insecticidally effective amount of acompound according to any one of claims 1, 2 to 9, 10 and 11 and anagriculturally suitable carrier therefor.
 13. A method of controllinginsects comprising contacting them or their environment with aneffective amount of a compound according to any one of claims 1, 2 to 9,10 and 11.